Herbicides

ABSTRACT

Compounds of formula (I), wherein the substituents are as defined in claim  1 , and the agrochemically acceptable salts and all stereoisomers and tautomeric forms of the compounds of formula I are suitable for use as herbicides.

The present invention relates to novel, herbicidally active nicotinoylderivatives, to processes for their preparation, to compositionscomprising those compounds, and to their use in controlling weeds,especially in crops of useful plants, or in inhibiting plant growth.

Nicotinoyl derivatives having herbicidal action are described, forexample, in WO 00/15615 and WO 01/94339.

There have now been found novel nicotinoyl derivatives having herbicidaland growth-inhibiting properties, the structures of which aredistinguished by a double bond in the 6,7-position of thebicyclo[3.2.1]oct-3-en-2-one, bicyclo[3.2.1]nona-3-en-2-one,8-oxa-bicyclo-[3.2.1]octa-3-en-2-one,8-aza-bicyclo[3.2.1]octa-3-en-2-one,8-thia-bicyclo[3.2.1]octa-3-en-2-one andbicyclo[3.2.1]octa-3-ene-2,8-dione group. Some of the compounds of thatkind are covered by WO 00/15615 but none of those compounds isspecifically disclosed. WO 01/66522 includes pyridine ketones havingbicyclo[3.2.1]oct-3-en-2-one groups as intermediates in the preparationof aroyl ketones. There is no mention therein of those compounds havinga herbicidal action.

The present invention accordingly relates to compounds of formula I

wherein

-   Y is oxygen, NR_(4a), sulfur, sulfonyl, sulfinyl, C(O), C(═NR_(4b)),    C(═CR_(6a)R_(6b)) or a C₁-C₄alkylene or C₂-C₄alkenylene chain, which    may be interrupted by oxygen, NR_(5a), sulfur, sulfonyl, sulfinyl,    C(O) or C(═NR_(5b)) and/or mono- or poly-substituted by R₆;-   A₁ is nitrogen or CR₇;-   A₂ is nitrogen or CR₈;-   R₁, R₂, R₆, R₇ and R₈ are each independently of the others hydrogen,    hydroxy, mercapto, NO₂, cyano, halogen, formyl, oxyiminomethylene,    C₁-C₆alkoxyiminomethylene, C₁-C₆alkyl, C₁-C₆haloalkyl, C₂-C₆alkenyl,    C₂-C₆haloalkenyl, C₂-C₆alkynyl, C₂-C₆haloalkynyl, C₁-C₆alkoxy,    C₁-C₆haloalkoxy, C₃-C₆alkenyloxy, C₃-C₆alkynyloxy,    C₃-C₆oxacycloalkyl, C₃-C₆thiacycloalkyl, C₃-C₆dioxacycloalkyl,    C₃-C₆dithiacycloalkyl, C₃-C₆oxathiacycloalkyl, C₁-C₆alkoxycarbonyl,    C₁-C₆alkylcarbonyl, C₁-C₆alkoxycarbonyloxy, C₁-C₆alkylcarbonyloxy,    C₁-C₆alkylthio, C₁-C₆alkylsulfonyl, C₁-C₆alkylsulfinyl, NR₉R₁₀,    C₃-C₆cycloalkyl, tri(C₁-C₆alkyl)silyl, di(C₁-C₆alkyl)phenylsilyl,    tri(C₁-C₆alkyl)silyloxy, di(C₁-C₆alkyl)phenylsilyloxy or Ar₁;-   or R₁, R₂, R₆, R₇, R₈ are each independently of the others a    C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl or C₃-C₆cycloalkyl group,    which may be interrupted by oxygen, sulfur, sulfonyl, sulfinyl,    —NR₁₁— or —C(O)— and/or mono-, di- or tri-substituted by hydroxy,    mercapto, NO₂, cyano, halogen, formyl, C₁-C₆alkoxy, C₃-C₆alkenyloxy,    C₃-C₆alkynyloxy, C₁-C₆haloalkoxy, C₁-C₂alkoxy-C₁-C₂alkoxy,    C₁-C₄alkoxycarbonyloxy, C₁-C₄alkylcarbonyloxy, C₁-C₄alkoxy-carbonyl,    C₁-C₄alkylcarbonyl, C₁-C₆alkylthio, C₁-C₆alkylsulfinyl,    C₁-C₆alkylsulfonyl, NR₁₂R₁₃, C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl,    C₃-C₆cycloalkyl, tri(C₁-C₆alkyl)silyl, tri(C₁-C₆alkyl)-silyloxy or    Ar₂;-   or two substituents R₆ at the same carbon atom together form a    —CH₂O— or a C₂-C₅alkylene chain, which may be interrupted once or    twice by oxygen, sulfur, sulfinyl or sulfonyl and/or mono- or    poly-substituted by R_(6c), with the proviso that two hetero atoms    may not be located next to one another;-   or two substituents R₆ at different carbon atoms together form an    oxygen bridge or a C₁-C₄alkylene chain, which may in turn be    substituted by R_(6c);-   or R₇ and R₈ together form a —CH₂CH═CH—, —OCH═CH— or —CH═CH—CH═CH—    bridge or a C₃-C₄alkylene chain, which may be interrupted by oxygen    or —S(O)_(n1)— and/or mono- or poly-substituted by R_(6d);-   R₃ is hydroxy, halogen, mercapto, C₁-C₈alkylthio,    C₁-C₈alkylsulfinyl, C₁-C₈alkylsulfonyl, C₁-C₈haloalkylthio,    C₁-C₈haloalkylsulfinyl, C₁-C₈haloalkylsulfonyl,    C₁-C₄alkoxy-C₁-C₄alkylthio, C₁-C₄alkoxy-C₁-C₄alkylsulfinyl,    C₁-C₄alkoxy-C₁-C₄alkylsulfonyl, C₃-C₈alkenylthio, C₃-C₈-alkynylthio,    C₁-C₄alkylthio-C₁-C₄alkylthio, C₃-C₄alkenylthio-C₁-C₄alkylthio,    C₁-C₄alkoxycarbonyl-C₁-C₄alkylthio,    C₁-C₄alkoxycarbonyl-C₁-C₄alkylsulfinyl,    C₁-C₄alkoxycarbonyl-C₁-C₄alkylsulfonyl, C₃-C₈cycloalkylthio,    C₃-C₈cycloalkylsulfinyl, C₃-C₈cycloalkylsulfonyl,    phenyl-C₁-C₄alkylthio, phenyl-C₁-C₄alkylsulfinyl,    phenyl-C₁-C₄alkylsulfonyl, S(O)n₁—Ar₃, phenylthio, phenylsulfinyl,    phenylsulfonyl, it being possible for the phenyl-containing groups    to be substituted by one or more C₁-C₃alkyl, C₁-C₃haloalkyl,    C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₄alkoxycarbonyl, halogen, cyano,    hydroxy or nitro groups;-   or R₃ is O⁻M⁺, wherein M⁺ is an alkali metal cation or an ammonium    cation;-   Q is a radical

-   p₁, p₂ and p₃ are 0 or 1;-   m₁, m₂ and m₃ are 1, 2 or 3;-   X₁, X₂ and X₃ are hydroxy, halogen, C₁-C₆alkyl, C₁-C₆haloalkyl,    C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₂-C₆alkynyl, C₂-C₆haloalkynyl,    C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₁-C₆alkylthio, C₁-C₆alkylsulfinyl,    C₁-C₆alkylsulfonyl, C₁-C₆haloalkylthio, C₁-C₆haloalkylsulfinyl or    C₁-C₆haloalkylsulfonyl;-   Z₁, Z₂ and Z₃ are C₁-C₆alkyl which is substituted by the following    substituents: C₃-C₄cycloalkyl or C₃-C₄cycloalkyl substituted by    halogen, C₁-C₆alkyl, C₁-C₃alkoxy or C₁-C₃alkoxy-C₁-C₃alkyl; oxiranyl    or oxiranyl substituted by C₁-C₆alkyl or C₁-C₃alkoxy-C₁-C₃alkyl;    3-oxetanyl or 3-oxetanyl substituted by C₁-C₆alkyl, C₁-C₃alkoxy or    C₁-C₃alkoxy-C₁-C₃alkyl; 3-oxetanyloxy or 3-oxetanyloxy substituted    by C₁-C₆alkyl, C₁-C₃alkoxy or C₁-C₃alkoxy-C₁-C₃alkyl;    C₃-C₆cycloalkyloxy or C₃-C₄cycloalkyloxy substituted by halogen,    C₁-C₆alkyl, C₁-C₃alkoxy or C₁-C₃alkoxy-C₁-C₃alkyl; C₁-C₆haloalkoxy;    C₁-C₆alkylsulfonyloxy; C₁-C₆haloalkylsulfonyloxy; phenylsulfonyloxy;    benzylsulfonyloxy; benzoyloxy; phenoxy; phenylthio; phenylsulfinyl;    phenylsulfonyl; Ar₁₀; OAr₁₂; tri(C₁-C₆alkyl)silyl or    tri(C₁-C₆alkyl)silyloxy, it being possible for the phenyl-containing    groups to be mono- or poly-substituted by C₁-C₃alkyl,    C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano,    hydroxy or nitro;-   or Z₁, Z₂ and Z₃ are 3-oxetanyl; 3-oxetanyl substituted by    C₁-C₃alkoxy, C₁-C₃alkoxy-C₁-C₃-alkyl or C₁-C₆alkyl; C₃-C₆cycloalkyl    substituted by halogen, C₁-C₃alkyl or C₁-C₃alkoxy-C₁-C₃-alkyl;    tri(C₁-C₆alkyl)silyl; tri(C₁-C₆alkyl)silyloxy or CH═P(phenyl)₃;-   or Z₁, Z₂ and Z₃ are a C₁-C₆alkyl, C₂-C₆alkenyl or C₂-C₆alkynyl    group, which is interrupted by oxygen, —O(CO)—, —(CO)O—, —O(CO)O—,    —N(R₁₄)O—, —ONR₁₅—, sulfur, sulfinyl, sulfonyl, —SO₂NR₁₆—, —NR₁₇SO₂—    or —NR₁₈— and is mono- or poly-substituted by L₁; it also being    possible for L₁ to be bonded at the terminal carbon atom of the    C₁-C₆alkyl, C₂-C₆alkenyl or C₂-C₆alkynyl group;-   or Z₁, Z₂ and Z₃ are hydrogen, hydroxy, mercapto, NO₂, cyano,    halogen, formyl, C₁-C₆alkyl, C₁-C₆haloalkyl, C₂-C₆alkenyl,    C₂-C₆haloalkenyl, C₂-C₆alkynyl, C₂-C₆haloalkynyl, C₁-C₆alkoxy,    C₁-C₆haloalkoxy, C₁-C₆alkoxycarbonyl, C₁-C₆alkylcarbonyl,    C₁-C₆alkylthio, C₁-C₆alkylsulfonyl, C₁-C₆alkylsulfinyl, NR₂₂R₂₃,    phenyl which may be mono- or poly-substituted by C₁-C₃alkyl,    C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano,    hydroxy or nitro, C₃-C₆cycloalkyl, C₅-C₆cycloalkyl substituted by    C₁-C₃alkoxy, C₁-C₃alkoxy-C₁-C₃alkyl or C₁-C₆alkyl, or Ar₅, O—Ar₆,    N(R₂₄)Ar₇ or S(O)n₆Ar₈;-   L₁ is hydrogen, halogen, hydroxy, amino, formyl, nitro, cyano,    mercapto, carbamoyl, P(O)(OC₁-C₆alkyl)₂, C₁-C₆alkoxy,    C₁-C₆haloalkoxy, C₁-C₆alkoxycarbonyl, C₂-C₆alkenyl,    C₂-C₆haloalkenyl, C₂-C₆alkynyl, C₂-C₆haloalkynyl, C₃-C₆cycloalkyl,    halo-substituted C₃-C₆cycloalkyl, C₃-C₆alkenyloxy, C₃-C₆alkynyloxy,    C₃-C₆haloalkenyloxy, cyano-C₁-C₆alkoxy, C₁-C₆alkoxy-C₁-C₆alkoxy,    C₁-C₆alkylthio-C₁-C₆alkoxy, C₁-C₆alkylsulfinyl-C₁-C₆alkoxy,    C₁-C₆alkylsulfonyl-C₁-C₆alkoxy, C₁-C₆alkoxycarbonyl-C₁-C₆alkoxy,    C₁-C₆alkylcarbonyloxy-C₁-C₆alkylcarbonyl, C₁-C₆alkylthio,    C₁-C₆alkylsulfinyl, C₁-C₆alkylsulfonyl, C₁-C₆haloalkylthio,    C₁-C₆haloalkylsulfinyl, C₁-C₆haloalkylsulfonyl or oxiranyl, which    may in turn be substituted by C₁-C₆alkyl, C₁-C₃alkoxy or    C₁-C₃alkoxy-C₁-C₃alkyl, or (3-oxetanyl)-oxy, which may in turn be    substituted by C₁-C₆alkyl, C₁-C₃alkoxy or C₁-C₃alkoxy-C₁-C₃alkyl, or    benzoyloxy, benzyloxy, benzylthio, benzylsulfinyl, benzylsulfonyl,    C₁-C₆alkylamino, di(C₁-C₆alkyl)amino, R₁₉S(O)₂O—, R₂₀N(R₂₁)SO₂—,    rhodano, phenyl, phenoxy, phenylthio, phenylsulfinyl,    phenylsulfonyl, Ar₄ or OAr₁₁, it being possible for the    phenyl-containing groups in turn to be substituted by one or more    C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen,    cyano, hydroxy or nitro groups;-   R_(4a) and R_(5a) are each independently of the other hydrogen,    C₁-C₆alkyl, C₁-C₆haloalkyl, cyano, formyl, C₁-C₆alkylcarbonyl,    C₁-C₆alkoxycarbonyl, carbamoyl, C₁-C₆alkylaminocarbonyl,    di(C₁-C₆alkylamino)carbonyl, di(C₁-C₆alkylamino)sulfonyl,    C₃-C₆cycloalkylcarbonyl, C₁-C₆-alkylsulfonyl, phenylcarbonyl,    phenylaminocarbonyl or phenylsulfonyl, it being possible for the    phenyl groups to be mono- or poly-substituted by C₁-C₆alkyl,    C₁-C₆haloalkyl, C₁-C₆-alkoxy, C₁-C₆haloalkoxy, halogen, cyano,    hydroxy or nitro;-   R_(4b) and R_(5b) are each independently of the other hydroxy,    C₁-C₆alkoxy, C₃-C₆alkenyloxy, C₃-C₆alkynyloxy or benzyloxy, it being    possible for the benzyl group to be mono- or poly-substituted by    C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, halogen,    cyano, hydroxy or nitro;-   R₉, R₁₁, R₁₃, R₁₆, R₁₇, R₁₈, R₂₀, R₂₃ and R₂₄ are each independently    of the others hydrogen, C₁-C₆alkyl, Ar₉, C₁-C₆haloalkyl,    C₁-C₆alkylcarbonyl, C₁-C₆alkoxycarbonyl, C₁-C₆alkylsulfonyl, phenyl,    it being possible for the phenyl group in turn to be mono- or    poly-substituted by C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxy,    C₁-C₆haloalkoxy, halogen, cyano, hydroxy or nitro;-   R_(6a) is hydrogen, C₁-C₆alkyl or C₁-C₆alkylcarbonyl; or together    with R_(6b) is a C₂-C₅alkylene chain;-   R_(6b), R_(6d), R₁₀, R₁₂ and R₂₂ are each independently of the    others hydrogen or C₁-C₆alkyl;-   R_(6c), R₁₄, R₁₅, R₁₉ and R₂₁ are each independently of the others    C₁-C₆alkyl or C₁-C₆haloalkyl;-   Ar₁, Ar₂, Ar₃, Ar₄, Ar₅, Ar₆, Ar₇, Ar₈, Ar₉, Ar₁₀, Ar₁₁ and Ar₁₂ are    each independently of the others a five- to ten-membered, monocyclic    or fused bicyclic ring system, which may be aromatic, partially    saturated or fully saturated and may contain from 1 to 4 hetero    atoms selected from nitrogen, oxygen, sulfur, C(O) and C(═NR₂₅), and    each ring system may contain not more than two oxygen atoms, not    more than two sulfur atoms, not more than two C(O) groups and not    more than one C(═NR₂₅) group, and each ring system may itself be    mono- or poly-substituted by C₁-C₆alkyl, C₁-C₆haloalkyl,    C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₂-C₆alkynyl, C₂-C₆haloalkynyl,    C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₃-C₆alkenyloxy, C₃-C₆alkynyloxy,    mercapto, amino, hydroxy, C₁-C₆alkylthio, C₁-C₆haloalkylthio,    C₃-C₆alkenylthio, C₃-C₆-haloalkenylthio, C₃-C₆alkynylthio,    C₁-C₃alkoxy-C₁-C₃alkylthio, C₁-C₄alkylcarbonyl-C₁-C₃alkylthio,    C₁-C₄alkoxycarbonyl-C₁-C₃alkylthio, cyano-C₁-C₃alkylthio,    C₁-C₆alkylsulfinyl, C₁-C₆haloalkylsulfinyl, C₁-C₆alkylsulfonyl,    C₁-C₆haloalkylsulfonyl, aminosulfonyl, C₁-C₂alkylaminosulfonyl,    N,N-di(C₁-C₂alkyl)aminosulfonyl, di(C₁-C₄alkyl)amino, halogen,    cyano, nitro or phenyl, it being possible for the phenyl group in    turn to be substituted by hydroxy, C₁-C₆-alkylthio,    C₁-C₆haloalkylthio, C₃-C₆alkenylthio, C₃-C₆haloalkenylthio,    C₃-C₆alkynylthio, C₁-C₃alkoxy-C₁-C₃alkylthio,    C₁-C₄alkylcarbonyl-C₁-C₃alkylthio,    C₁-C₄alkoxycarbonyl-C₁-C₃-alkylthio, cyano-C₁-C₃alkylthio,    C₁-C₆alkylsulfinyl, C₁-C₆haloalkylsulfinyl, C₁-C₆alkylsulfonyl,    C₁-C₆haloalkylsulfonyl, aminosulfonyl, C₁-C₂alkylaminosulfonyl,    N,N-di(C₁-C₂alkyl)aminosulfonyl, di(C₁-C₄alkyl)amino, halogen, cyano    or nitro, and the substituents at the nitrogen atom in the    heterocyclic ring being other than halogen, and two oxygen atoms not    being located next to one another;-   R₂₅ is hydrogen, hydroxy, C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxy,    C₁-C₆alkylcarbonyl, C₁-C₆alkoxycarbonyl or C₁-C₆alkylsulfonyl; and-   n₁ is 0, 1 or 2; and n₆ is 0, 1 or 2;-   and agronomically acceptable salts/isomers/enantiomers/tautomers of    those compounds.

The alkyl groups appearing in the substituent definitions may bestraight-chain or branched and are, for example, methyl, ethyl,n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl,hexyl, heptyl and octyl and the branched isomers thereof. Alkoxy,alkenyl and alkynyl radicals are derived from the mentioned alkylradicals. The alkenyl and alkynyl groups may be mono- orpoly-unsaturated. C₁-C₄alkylene and C₂-C₄alkenylene chains may likewisebe straight-chain or branched.

Halogen is generally fluorine, chlorine, bromine or iodine, preferablyfluorine or chlorine. The same is true of halogen in conjunction withother meanings, such as haloalkyl or halophenyl.

Haloalkyl groups preferably have a chain length of from 1 to 6 carbonatoms. Haloalkyl is, for example, fluoromethyl, difluoromethyl,trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl,2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl,1,1-difluoro-2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl or2,2,2-trichloroethyl; preferably trichloromethyl, difluorochloromethyl,difluoromethyl, trifluoromethyl or dichlorofluoromethyl.

In the context of the present invention, the term “mono- orpoly-substituted” is generally to be understood as meaning mono- topenta-substituted, especially mono- to tri-substituted.

As haloalkenyl there come into consideration alkenyl groups mono- orpoly-substituted by halogen, halogen being fluorine, chlorine, bromineor iodine, and especially fluorine or chlorine, for example2,2-difluoro-1-methylvinyl, 3-fluoropropenyl, 3-chloropropenyl,3-bromopropenyl, 2,3,3-trifluoropropenyl, 2,3,3-trichloropropenyl and4,4,4-trifluoro-but-2-en-1-yl. Of the C₃-C₈alkenyl groups mono-, di- ortri-substituted by halogen preference is given to those having a chainlength of from 3 to 5 carbon atoms.

As haloalkynyl there come into consideration, for example, alkynylgroups mono- or poly-substituted by halogen, halogen being bromine,iodine and especially fluorine or chlorine, for example3-fluoropropynyl, 3-chloropropynyl, 3-bromopropynyl,3,3,3-trifluoropropynyl and 4,4,4-trifluoro-but-2-yn-1-yl. Of thealkynyl groups mono- or poly-substituted by halogen preference is givento those having a chain length of from 3 to 5 carbon atoms.

Ar₁, Ar₂, Ar₃, Ar₄, Ar₅, Ar₆, Ar₇, A₈, A₉, Ar₁₀, Ar₁₁ and Ar₁₂ are, forexample, phenyl, naphthyl or the following heterocyclic groups:(1-methyl-1H-pyrazol-3-yl)-; (1-ethyl-1H-pyrazol-3-yl)-;(1-propyl-1H-pyrazol-3-yl)-; (1H-pyrazol-3-yl)-;(1,5-dimethyl-1H-pyrazol-3-yl)-; (4-chloro-1-methyl-1H-pyrazol-3-yl)-;(1H-pyrazol-1-yl)-; (3-methyl-1H-pyrazol-1-yl)-;(3,5-dimethyl-1H-pyrazol-1-yl)-; (3-isoxazolyl)-;(5-methyl-3-isoxazolyl)-; (3-methyl-5-isoxazolyl)-; (5-isoxazolyl)-;(1H-pyrrol-2-yl)-; (1-methyl-1H-pyrrol-2-yl)-; (1H-pyrrol-1-yl)-;(1-methyl-1H-pyrrol-3-yl)-; (2-furanyl)-; (5-methyl-2-furanyl)-;(3-furanyl)-; (5-methyl-2-thienyl)-; (2-thienyl)-; (3-thienyl)-;(1-methyl-1H-imidazol-2-yl)-; (1H-imidazol-2-yl)-;(1-methyl-1H-imidazol-4-yl)-; (1-methyl-1H-imidazol-5-yl)-;(4-methyl-2-oxazolyl)-; (5-methyl-2oxazolyl)-; (2-oxazolyl)-;(2-methyl-5-oxazolyl)-; (2-methyl-4-oxazolyl)-; (4-methyl-2-thiazolyl)-;(5-methyl-2-thiazolyl)-; (2-thiazolyl)-; (2-methyl-5-thiazolyl)-;(2-methyl-4-thiazolyl)-; (3-methyl-4-isothiazolyl)-;(3-methyl-5-isothiazolyl)-; (5-methyl-3-isothiazolyl)-;(1-methyl-1H-1,2,3-triazol-4-yl)-; (2-methyl-2H-1,2,3-triazol-4-yl)-;(4-methyl-2H-1,2,3-triazol-2-yl)-; (1-methyl-1H-1,2,4-triazol-3-yl)-;(1,5-dimethyl-1H-1,2,4-triazol-3-yl)-;(3-methyl-1H-1,2,4-triazol-1-yl)-; (5-methyl-1H-1,2,4-triazol-1-yl)-;(4,5-dimethyl-4H-1,2,4-triazol-3-yl)-;(4-methyl-4H-1,2,4-triazol-3-yl)-; (4H-1,2,4-triazol-4-yl)-;(5-methyl-1,2,3-oxadiazol-4-yl)-; (1,2,3-oxadiazol-4-yl)-;(3-methyl-1,2,4-oxadiazol-5-yl)-; (5-methyl-1,2,4-oxadiazol-3-yl)-;(4-methyl-3-furazanyl)-; (3-furazanyl)-;(5-methyl-1,2,4-oxadiazol-2-yl)-; (5-methyl-1,2,3-thiadiazol-4-yl)-;(1,2,3-thiadiazol-4-yl)-; (3-methyl-1,2,4-thiadiazol-5-yl)-;(5-methyl-1,2,4-thiadiazol-3-yl)-; (4-methyl-1,2,5-thiadiazol-3-yl)-;(5-methyl-1,3,4-thiadiazol-2-yl)-; (1-methyl-1H-tetrazol-5-yl)-;(1H-tetrazol-5-yl)-; (5-methyl-1H-tetrazol-1-yl)-;(2-methyl-2H-tetrazol-5-yl)-; (2-ethyl-2H-tetrazol-5-yl)-;(5-methyl-2H-tetrazol-2-yl)-; (2H-tetrazol-2-yl)-; (2-pyridyl)-;(6-methyl-2-pyridyl)-; (4-pyridyl)-; (3-pyridyl)-;(6-methyl-3-pyridazinyl)-; (5-methyl-3-pyridazinyl)-; (3-pyridazinyl)-;(4,6-dimethyl-2-pyrimidinyl)-; (4-methyl-2-pyrimidinyl)-;(2-pyrimidinyl)-; (2-methyl-4-pyrimidinyl)-; (2-chloro-4-pyrimidinyl)-;(2,6-dimethyl-4-pyrimidinyl)-; (4-pyrimidinyl)-;(2-methyl-5-pyrimidinyl)-; (6-methyl-2-pyrazinyl)-; (2-pyrazinyl)-;(4,6-dimethyl-1,3,5-triazin-2-yl)-; (4,6-dichloro-1,3,5-triazin-2-yl)-;(1,3,5-triazin-2-yl)-; (4-methyl-1,3,5-triazin-2-yl)-;(3-methyl-1,2,4-triazin-5-yl)-; (3-methyl-1,2,4-triazin-6-yl)-;

and Ar₁₀ may also be, for example, a carbonyl-containing heterocyclicgroup

wherein each R₂₆ is methyl, each R₂₇ and each R₂₈ are independentlyhydrogen, C₁-C₃alkyl, C₁-C₃alkoxy, C₁-C₃alkylthio or trifluoromethyl, X₄is oxygen or sulfur and r=1, 2, 3 or 4.

Where no free valency is indicated in those definitions of Ar₁, Ar₂,Ar₃, Ar₄, Ar₅, Ar₆, Ar₇, Ar₈, A₉, Ar₁₀, Ar₁₁ and Ar₁₂, for example as in

the linkage site is located at the carbon atom labelled “CH” or in acase such as, for example,

at the bonding site indicated at the bottom left.

The alkali metal cation M⁺ (for example in the meaning of O⁻M⁺ in R₃)denotes in the context of the present invention preferably the sodiumcation or the potassium cation.

Alkoxy groups preferably have a chain length of from 1 to 6 carbonatoms. Alkoxy is, for example, methoxy, ethoxy, propoxy, isopropoxy,n-butoxy, isobutoxy, sec-butoxy and tert-butoxy and the isomers ofpentyloxy and hexyloxy; preferably methoxy and ethoxy. Alkylcarbonyl ispreferably acetyl, propionyl or pivaloyl. Alkoxycarbonyl is, forexample, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl,isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl,sec-butoxycarbonyl or tert-butoxycarbonyl; preferably methoxycarbonyl orethoxycarbonyl. Haloalkoxy groups preferably have a chain length of from1 to 6 carbon atoms. Haloalkoxy is e.g. fluoromethoxy, difluoromethoxy,trifluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy,2-fluoroethoxy, 2-chloroethoxy, 2,2-difluoroethoxy and2,2,2-trichloroethoxy; preferably difluoromethoxy, 2-chloroethoxy andtrifluoromethoxy.

Alkylthio groups preferably have a chain length of from 1 to 8 carbonatoms. Alkylthio is, for example, methylthio, ethylthio, propylthio,isopropylthio, n-butylthio, isobutylthio, sec-butylthio ortert-butylthio, preferably methylthio and ethylthio. Alkylsulfinyl is,for example, methylsulfinyl, ethylsulfinyl, propylsulfinyl,isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl,tert-butylsulfinyl; preferably methylsulfinyl and ethylsulfinyl.Alkylsulfonyl is, for example, methylsulfonyl, ethylsulfonyl,propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl,sec-butylsulfonyl or tert-butylsulfonyl; preferably methylsulfonyl orethylsulfonyl.

Alkylamino is, for example, methylamino, ethylamino, n-propylamino,isopropylamino or the isomers of butylamine. Dialkylamino is, forexample, dimethylamino, methylethylamino, diethylamino,n-propylmethylamino, di-butylamino and di-isopropylamino. Preference isgiven to alkylamino and dialkylamino groups—including as a component of(N-alkyl)sulfonylamino and N-(alkylamino)sulfonyl groups, such as(N,N-dimethyl)sulfonylamino and N,N-(dimethylamino)sulfonyl—each havinga chain length of from 1 to 4 carbon atoms.

Alkoxyalkoxy groups preferably have a chain length of from 1 to 8 carbonatoms. Examples of alkoxyalkoxy are: methoxymethoxy, methoxyethoxy,methoxypropoxy, ethoxymethoxy, ethoxyethoxy, propoxymethoxy andbutoxybutoxy. Alkoxyalkyl groups have a chain length of preferably from1 to 6 carbon atoms. Alkoxyalkyl is, for example, methoxymethyl,methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl,n-propoxyethyl, isopropoxymethyl or isopropoxyethyl.

Alkylthioalkyl groups preferably have from 1 to 8 carbon atoms.Alkylthioalkyl is, for example, methylthiomethyl, methylthioethyl,ethylthiomethyl, ethylthioethyl, n-propylthiomethyl, n-propylthioethyl,isopropylthiomethyl, isopropylthioethyl, butylthiomethyl, butylthioethylor butylthiobutyl.

The cycloalkyl groups having up to 8 carbon atoms preferably have from 3to 6 ring carbon atoms, for example cyclopropyl, cyclobutyl,cyclopentyl, cyclohexyl. A cycloalkyl group having up to 8 carbon atomsalso includes a C₃-C₆alkyl group bonded by way of a methylene orethylene bridge, for example cyclopropylmethyl, cyclobutylmethyl andcyclopentylmethyl. Cycloalkyl groups, as well as, for example, theoxygen-containing oxiranyl, oxiranylmethyl, 3-oxetanyl, 2- and3-tetrahydrofuranyl, 2-(2- and 3-tetrahydrofuranyl)methyl, 2-, 3- and4-tetrahydropyranyl, 2-(2-tetrahydropyranyl)methyl, 1,3-dioxolanyl,2-(1,3-dioxolanyl)methyl, 4-(1,3-dioxolanyl)methyl, 1,3-dioxanyl,1,4-dioxanyl and similar saturated groups—especially as a component ofAr₅ in L₁—can also be mono- or poly-substituted by C₁-C₃alkyl,preferably mono- to tetra-substituted by methyl.

Phenyl, including as a component of a substituent such as phenoxy,benzyl, benzyloxy, benzoyl, phenylthio, phenylalkyl, phenoxyalkyl, maybe in substituted form. The substituents may in that case be in theortho-, meta- and/or para-position(s). Preferred substituent positionsare the ortho- and para-positions relative to the ring linkage site. Thephenyl groups are preferably unsubstituted or mono- or di-substituted,especially unsubstituted or mono-substituted.

Z₁, Z₂ and Z₃ as a C₁-C₆alkyl group which is interrupted by oxygen,—O(CO)—, —(CO)O—, —O(CO)O—, —N(R₁₄)O—, —ONR₁₅—, sulfur, sulfinyl,sulfonyl, —SO₂NR₁₆—, —NR₁₇SO₂— or —NR₁₈— and may be mono- orpoly-substituted by a group L₁ when that C₁-C₆alkyl group is interruptedby oxygen, —O(CO)O—, sulfur, sulfinyl or sulfonyl, is to be understoodas meaning, for example, a bidentate bridging member —CH₂OCH₂—,—CH₂CH₂OCH₂—, —CH₂OCH₂CH₂—, —CH₂OCH₂CH₂CH₂—, —CH₂OC(O)CH₂—,—CH₂(CO)OCH₂—, —CH₂O(CO)OCH₂—, —CH₂SCH₂—, —CH₂S(O)CH₂—, —CH₂SO₂CH₂—,—CH₂SCH₂CH₂—, —CH₂S(O)CH₂CH₂—, —CH₂SO₂CH₂CH₂—, —CH₂N(CH₃)SO₂CH₂—,—CH₂N(SO₂CH₃)CH₂—, —CH₂N(C(O)CH₃)CH₂—, —CH₂N(COOCH₂CH₃)CH₂— or—CH₂N(COOCH₃)CH₂—, the left-hand bonding site being bonded to thepyridine moiety and the right-hand side to the substituent L₁. And Z₁,Z₂ and Z₃ as a C₂-C₆alkenyl or C₂-C₆alkynyl group which is interruptedby oxygen, —O(CO)—, —(CO)O—, —O(CO)O—, —N(R₁₄)O—, —ONR₁₅—, sulfur,sulfinyl, sulfonyl, —SO₂NR₁₆—, —NR₁₇SO₂— or —NR₁₈— and may be mono- orpoly-substituted by a group L₁ is to be understood as meaning, forexample, a bidentate bridging member —CH═CHCH₂OCH₂— or —C≡CCH₂OCH₂—.Such an unsubstituted or L₁-substituted C₁-C₆alkyl, C₂-C₆alkenyl orC₂-C₆alkynyl group Z₁, Z₂ or Z₃ which is interrupted by oxygen, —O(CO)—,—(CO)O—, —O(CO)O—, —N(R₁₄)O—, —ONR₁₅—, sulfur, sulfinyl, sulfonyl,—SO₂NR₁₆—, —NR₁₇OS₂— or —NR₁₈— can be either straight-chain or branched,for example as in the case of the bidentate bridging members—CH(CH₃)OCH₂— and —CH₂OCH(CH₃)CH₂—.

The compounds of formula I may occur in various tautomeric forms suchas, for example, when R₃ is hydroxy and Q is Q₁, in formulae I′, I″, I′″and I″″, preference being given to formulae I′ and I″.

Since compounds of formula I may also contain asymmetric carbon atoms,for example in the case of R₁, R₂, A₁, A₂ and Y, their substituents R₆,R₇ and R₈, and also in the case of carbon atoms carrying X₁, X₂, X₃, Z₁,Z₂ and Z₃, and accordingly in any sulfoxides, all the stereoisomers andall chiral <R> and <S> forms are also included. Also included are allconstitutional isomeric <E> and <Z> forms in respect of any —C═C— and—C═N— double bonds.

Since R₁ and R₂, like R₇ and R₈ in A₁ and A₂, may each independently ofthe other have the same or different meanings, the compound of formula Imay also occur in various constitutional isomeric forms. The inventiontherefore relates also to all those constitutional isomeric forms inrespect of the spatial arrangement of A₁ and A₂ and the substituents R₁and R₂ in respect of the substituent R₃ as shown in formulae D₁ to D₄.

The same applies also to the spatial arrangement of the bridging memberY in respect of the carbon atoms carrying R₁ and R₂ when Y is aC₁-C₄alkylene or C₂-C₄alkenylene chain which may be interrupted byoxygen, NR_(5a), sulfur, sulfonyl, sulfinyl, C(O) or C(═NR_(5b)) and/ormono- or poly-substituted by R₆.

The substituent R₃ may also be located on the bridging member, as hasalready been shown above in formula I″ wherein R₃ is hydroxy. Thepresent invention relates also to those constitutional isomeric forms D₅

of the compounds of formula I.

That arrangement of A₁, A₂, Y and the substituents R₁, R₂, R₄, R₅, R₆,R₇ and R₈ relates accordingly also to all possible tautomeric andstereoisomeric forms of the compounds used as intermediates.

The present invention relates also to the salts which the compounds offormula I are able to form with amines, alkali metal and alkaline earthmetal bases or quaternary ammonium bases. Among the alkali metal andalkaline earth metal bases as salt formers, special mention should bemade of the hydroxides of lithium, sodium, potassium, magnesium, bariumand calcium, but especially the hydroxides of sodium, barium andpotassium.

Examples of amines suitable for ammonium salt formation include ammoniaas well as primary, secondary and tertiary C₁-C₁₈alkylamines,C₁-C₄hydroxyalkylamines and C₂-C₄-alkoxyalkylamines, for examplemethylamine, ethylamine, n-propylamine, isopropylamine, the fourbutylamine isomers, n-amylamine, isoamylamine, hexylamine, heptylamine,octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine,heptadecylamine, octadecylamine, methylethylamine, methylisopropylamine,methylhexylamine, methylnonylamine, methylpentadecylamine,methyloctadecylamine, ethylbutylamine, ethylheptylamine,ethyloctylamine, hexylheptylamine, hexyloctylamine, dimethylamine,diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine,di-n-amylamine, diisoamylamine, dihexylamine, diheptylamine,dioctylamine, ethanolamine, n-propanolamine, isopropanolamine,N,N-diethanolamine, N-ethylpropanolamine, N-butylethanolamine,allylamine, n-butenyl-2-amine, n-pentenyl-2-amine,2,3-dimethylbutenyl-2-amine, dibutenyl-2-amine, n-hexenyl-2-amine,propylenediamine, trimethylamine, triethylamine, tri-n-propylamine,triisopropylamine, tri-n-butylamine, triisobutylamine,tri-sec-butylamine, tri-n-amylamine, methoxyethylamine andethoxyethylamine; heterocyclic amines, for example pyridine, quinoline,isoquinoline, morpholine, piperidine, pyrrolidine, indoline,quinuclidine and azepine; primary arylamines, for example anilines,methoxyanilines, ethoxyanilines, o-, m- and p-toluidines,phenylenediamines, benzidines, naphthylamines and o-, m- andp-chloroanilines; but especially triethylamine, isopropylamine anddiisopropylamine.

Preferred quaternary ammonium bases suitable for salt formationcorrespond, for example, to the formula [N(R_(a)R_(b)R_(c)R_(d))]OHwherein R_(a), R_(b), R_(c) and R_(d) are each independently of theothers C₁-C₄alkyl. Further suitable tetraalkylammonium bases with otheranions can be obtained, for example, by anion exchange reactions.

Preference is given to compounds of formula I wherein

-   R₁, R₂, R₆, R₇ and R₈ are each independently of the others hydrogen,    hydroxy, mercapto, NO₂, cyano, halogen, formyl, C₁-C₆alkyl,    C₁-C₆haloalkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₂-C₆alkynyl,    C₂-C₆haloalkynyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₃-C₆alkenyloxy,    C₃-C₆alkynyloxy, C₃-C₆oxacycloalkyl, C₃-C₆thiacycloalkyl,    C₃-C₆dioxacycloalkyl, C₃-C₆dithiacycloalkyl, C₃-C₆oxathiacycloalkyl,    C₁-C₆alkoxycarbonyl, C₁-C₆alkylcarbonyl, C₁-C₆alkoxycarbonyloxy,    C₁-C₆alkylcarbonyloxy, C₁-C₆alkylthio, C₁-C₆alkylsulfonyl,    C₁-C₆alkylsulfinyl, NR₉R₁₀, C₃-C₆cycloalkyl, tri(C₁-C₆alkyl)silyl,    tri(C₁-C₆alkyl)silyloxy or Ar₁;-   or R₁, R₂, R₆, R₇, R₈ are each independently of the others a    C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl or C₃-C₆cycloalkyl group,    which may be interrupted by oxygen, sulfur, sulfonyl, sulfinyl,    —NR₁₁— or —C(O)— and/or mono-, di- or tri-substituted by hydroxy,    mercapto, NO₂, cyano, halogen, formyl, C₁-C₆alkoxy, C₃-C₆alkenyloxy,    C₃-C₆alkynyloxy, C₁-C₆haloalkoxy, C₁-C₂alkoxy-C₁-C₂alkoxy,    C₁-C₄alkoxycarbonyloxy, C₁-C₄alkylcarbonyloxy, C₁-C₄alkoxycarbonyl,    C₁-C₄alkylcarbonyl, C₁-C₆alkylthio, C₁-C₆alkylsulfinyl,    C₁-C₆alkylsulfonyl, NR₁₂R₁₃, C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl,    C₃-C₆cycloalkyl, tri(C₁-C₆alkyl)silyl, tri(C₁-C₆alkyl)silyloxy or    Ar₂;-   or two substituents R₆ at the same carbon atom together form a    —CH₂O— or a C₂-C₅alkylene chain, which may be interrupted once or    twice by oxygen, sulfur, sulfonyl or sulfinyl and/or mono- or    poly-substituted by R_(6c), with the proviso that two hetero atoms    may not be located next to one another;-   or two substituents R₆ at different carbon atoms together form an    oxygen bridge or a C₁-C₄alkylene chain, which may in turn be    substituted by R_(6c);-   or R₇ and R₈ together form an oxygen bridge, a —CH═CH—CH═CH— bridge    or a C₃-C₄alkylene chain, which may be interrupted by oxygen or    —S(O)_(n1)— and/or mono- or poly-substituted by R_(6d);-   Z₁, Z₂ and Z₃ are each independently of the others    C₁-C₃alkoxy-C₁-C₃alkyl-substituted C₃-C₆cycloalkyl,    tri(C₁-C₆alkyl)silyl, tri(C₁-C₆alkyl)silyloxy or CH═P(phenyl)₃;-   or Z₁, Z₂ and Z₃ are a C₁-C₆alkyl, C₂-C₆alkenyl or C₂-C₆alkynyl    group, which is interrupted by oxygen, —O(CO)—, —(CO)O—, —O(CO)O—,    —N(R₁₄)—O—, —O—NR₁₅—, sulfur, sulfinyl, sulfonyl, —SO₂NR₁₆—,    —NR₁₇SO₂— or —NR₁₈— and is mono- or poly-substituted by L₁;-   L₁ is halogen, hydroxy, amino, formyl, nitro, cyano, mercapto,    carbamoyl, P(O)(OC₁-C₆alkyl)₂, C₁-C₆alkoxy, C₁-C₆haloalkoxy,    C₁-C₆alkoxycarbonyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₂-C₆alkynyl,    C₂-C₆haloalkynyl, C₃-C₆cycloalkyl, halo-substituted    C₃-C₆-cycloalkyl, C₃-C₆alkenyloxy, C₃-C₆alkynyloxy,    C₃-C₆haloalkenyloxy, cyano-C₁-C₆alkoxy, C₁-C₆alkoxy-C₁-C₆alkoxy,    C₁-C₆alkylthio-C₁-C₆alkoxy, C₁-C₆alkylsulfinyl-C₁-C₆alkoxy,    C₁-C₆alkylsulfonyl-C₁-C₆alkoxy, C₁-C₆alkoxycarbonyl-C₁-C₆alkoxy,    C₁-C₆alkylcarbonyloxy-C₁-C₆alkylcarbonyl, C₁-C₆alkylthio,    C₁-C₆alkylsulfinyl, C₁-C₆alkylsulfonyl, C₁-C₆haloalkylthio,    C₁-C₆haloalkylsulfinyl, C₁-C₆haloalkylsulfonyl or oxiranyl, which    may in turn be substituted by C₁-C₆alkyl, C₁-C₃alkoxy or    C₁-C₃alkoxy-C₁-C₃alkyl, or (3-oxetanyl)-oxy, which may in turn be    substituted by C₁-C₆alkyl, C₁-C₃alkoxy or C₁-C₃alkoxy-C₁-C₃alkyl, or    benzoyloxy, benzyloxy, benzylthio, benzylsulfinyl, benzylsulfonyl,    C₁-C₆alkylamino, di(C₁-C₆alkyl)amino, R₁₉S(O)₂O, R₂₀N(R₂₁)SO₂—,    rhodano, phenyl, phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl    or Ar₄, it being possible for the phenyl-containing groups in turn    to be substituted by one or more C₁-C₃alkyl, C₁-C₃haloalkyl,    C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano, hydroxy or nitro    groups;-   or, when R₁ and R₂ are hydrogen, methyl, halogen or    C₁-C₃alkoxycarbonyl and at the same time Y is other than    C₁-C₂alkylene which may be substituted by hydrogen, halogen or    methyl, or is other than oxygen, sulfur, sulfonyl, sulfinyl, C(O) or    NR_(4a) wherein R_(4a) is hydrogen, C₁-C₄alkyl, formyl or    C₁-C₄alkylcarbonyl,-   L₁ may additionally be hydrogen and Z₁, Z₂ and Z₃ may additionally    be hydrogen, hydroxy, mercapto, NO₂, cyano, halogen, formyl,    C₁-C₆alkyl, C₁-C₆haloalkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl,    C₂-C₆alkynyl, C₂-C₆haloalkynyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy,    C₁-C₆alkoxycarbonyl, C₁-C₆alkylcarbonyl, C₁-C₆alkylthio,    C₁-C₆alkylsulfonyl, C₁-C₆alkylsulfinyl, NR₂₂R₂₃, phenyl which may be    mono- or poly-substituted by C₁-C₃alkyl, C₁-C₃haloalkyl,    C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano, hydroxy or nitro, or    C₃-C₆cycloalkyl, C₃-C₆cycloalkyl substituted by C₁-C₃alkoxy,    C₁-C₃alkoxy-C₁-C₃alkyl or C₁-C₆alkyl, 3-oxetanyl, 3-oxetanyl    substituted by C₁-C₃alkoxy, C₁-C₃alkoxy-C₁-C₃alkyl or C₁-C₆alkyl; or    Ar₅, O—Ar₆, N(R₂₄)Ar₇ or S(O)n₆Ar₈;-   R₉, R₁₁, R₁₃, R₂₃, R₁₆, R₁₇, R₁₈, R₂₀ and R₂₄ are each independently    of the others hydrogen, C₁-C₆alkyl, C₁-C₆haloalkyl,    C₁-C₆alkylcarbonyl, C₁-C₆alkoxycarbonyl, C₁-C₆alkylsulfonyl, phenyl,    it being possible for the phenyl group in turn to be mono- or    poly-substituted by C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxy,    C₁-C₆haloalkoxy, halogen, cyano, hydroxy or nitro, or Ar₉;-   R_(6a) and R_(6b) are each independently of the other hydrogen or    C₁-C₆alkyl; or R_(6a) and R_(6b) together are a C₂-C₅alkylene chain;-   R_(6c), R₁₄, R₁₅, R₁₉ and R₂₁ are each independently of the others    C₁-C₆alkyl or C₁-C₆haloalkyl;-   R_(6d), R₁₀, R₁₂ and R₂₂ are each independently of the others    hydrogen or C₁-C₆alkyl;-   Ar₁, Ar₂, Ar₃, Ar₄, Ar₅, Ar₆, Ar₇, A₈ and A₉ are each independently    of the others a five- to ten-membered, monocyclic or fused bicyclic    ring system, which may be aromatic, partially saturated or fully    saturated and may contain from 1 to 4 hetero atoms selected from    nitrogen, oxygen, sulfur, C(O) and C(═NR₂₅), and each ring system    contains not more than two oxygen atoms and not more than two sulfur    atoms, and each ring system may itself be mono- or poly-substituted    by C₁-C₆alkyl, C₁-C₆haloalkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl,    C₂-C₆alkynyl, C₂-C₆haloalkynyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy,    C₃-C₆alkenyloxy, C₃-C₆alkynyloxy, mercapto, amino, hydroxy,    C₁-C₆alkylthio, C₁-C₆haloalkylthio, C₃-C₆alkenylthio,    C₃-C₆-haloalkenylthio, C₃-C₆alkynylthio, C₁-C₃alkoxy-C₁-C₃alkylthio,    C₁-C₄alkylcarbonyl-C₁-C₃alkylthio,    C₁-C₄alkoxycarbonyl-C₁-C₃alkylthio, cyano-C₁-C₃alkylthio,    C₁-C₆alkylsulfinyl, C₁-C₆haloalkylsulfinyl, C₁-C₆alkylsulfonyl,    C₁-C₆haloalkylsulfonyl, aminosulfonyl, C₁-C₂alkylaminosulfonyl,    N,N-di(C₁-C₂alkyl)aminosulfonyl, di(C₁-C₄alkyl)amino, halogen,    cyano, nitro or phenyl, it being possible for the phenyl group in    turn to be substituted by hydroxy, C₁-C₆-alkylthio,    C₁-C₆haloalkylthio, C₃-C₆alkenylthio, C₃-C₆haloalkenylthio,    C₃-C₆alkynylthio, C₁-C₃-alkoxy-C₁-C₃alkylthio,    C₁-C₄alkylcarbonyl-C₁-C₃alkylthio,    C₁-C₄alkoxycarbonyl-C₁-C₃alkylthio, cyano-C₁-C₃alkylthio,    C₁-C₆alkylsulfinyl, C₁-C₆haloalkylsulfinyl, C₁-C₆alkylsulfonyl,    C₁-C₆haloalkylsulfonyl, aminosulfonyl, C₁-C₂alkylaminosulfonyl,    N,N-di(C₁-C₂alkyl)aminosulfonyl, di(C₁-C₄alkyl)amino, halogen, cyano    or nitro, and the substituents at the nitrogen atom in the    heterocyclic ring being other than halogen.

Special mention should be made of compounds of formula I wherein L₁ ishydrogen only when Z₁, Z₂ and Z₃ are a C₁-C₆alkyl group which isinterrupted by —O(CO)—, —(CO)O—, —N(R₁₄)O—, —ONR₁₅—, —SO₂NR₁₆—,—NR₁₇SO₂— or —NR₁₈—, or is a C₂-C₆alkenyl or C₂-C₆alkynyl group which isinterrupted by oxygen, —O(CO)—, —(CO)O—, —O(CO)O—, —N(R₁₄)O—, —ONR₁₅—,sulfur, sulfinyl, sulfonyl, —SO₂NR₁₆—, —NR₁₇SO₂— or —NR₁₈—; and when,further, either R₁ and R₂ are hydrogen or methyl, or R₁ is halogen or R₂is C₁-C₃alkoxycarbonyl, and at the same time Y is other thanC₁-C₂alkylene which may be substituted by halogen or methyl, or Y isother than oxygen, sulfur, sulfonyl, sulfinyl, C(O) or NR_(4a) whereinR_(4a) is hydrogen, C₁-C₄alkyl, formyl or C₁-C₄alkylcarbonyl.

An outstanding group of compounds of formula I comprises those compoundswherein Z₁, Z₂, Z₃ are C₁-C₃alkylene which is substituted by thefollowing substituents: halogen, hydroxy, amino, formyl, nitro, cyano,mercapto, carbamoyl, P(O)(OC₁-C₆alkyl)₂, C₁-C₆alkoxy, C₁-C₆haloalkoxy,C₁-C₆alkoxycarbonyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₂-C₆alkynyl,C₂-C₆-haloalkynyl, C₃-C₆cycloalkyl, halo-substituted C₃-C₆cycloalkyl,C₃-C₆alkenyloxy, C₃-C₆alkynyloxy, C₃-C₆haloalkenyloxy,cyano-C₁-C₆alkoxy, C₁-C₆alkoxy-C₁-C₆alkoxy, C₁-C₆alkylthio-C₁-C₆alkoxy,C₁-C₆alkylsulfinyl-C₁-C₆alkoxy, C₁-C₆alkylsulfonyl-C₁-C₆alkoxy,C₁-C₆alkoxy-carbonyl-C₁-C₆alkoxy, C₁-C₆alkylcarbonyloxy,C₁-C₆alkylcarbonyl, C₁-C₆alkylthio, C₁-C₆alkylsulfinyl,C₁-C₆alkylsulfonyl, C₁-C₆haloalkylthio, C₁-C₆haloalkylsulfinyl,C₁-C₆haloalkylsulfonyl or oxiranyl, which may in turn be substituted byC₁-C₃alkyl, C₁-C₃alkoxy or C₁-C₃alkoxy-C₁-C₃alkyl, or (3-oxetanyl)-oxy,which may in turn be substituted by C₁-C₆alkyl, C₁-C₃alkoxy orC₁-C₃alkoxy-C₁-C₃alkyl, or benzoyloxy, benzyloxy, benzylthio,benzylsulfinyl, benzylsulfonyl, C₁-C₆alkylamino, di(C₁-C₆alkyl)amino,R₁₉S(O)₂O, R₂₀N(R₂₁)SO₂—, rhodano, phenyl, phenoxy, phenylthio,phenylsulfinyl, phenylsulfonyl or Ar₄, it being possible for thephenyl-containing groups in turn to be substituted by one or moreC₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃-alkoxy, C₁-C₃haloalkoxy, halogen,cyano, hydroxy or nitro groups;

-   or, when R₁ and R₂ are hydrogen, methyl, halogen or    C₁-C₃alkoxycarbonyl and at the same time Y is other than    C₁-C₂alkylene which may be substituted by halogen or methyl, or is    other than oxygen, sulfur, sulfonyl, sulfinyl, C(O) or NR_(4a)    wherein R_(4a) is hydrogen, C₁-C₄-alkyl, formyl or    C₁-C₄alkylcarbonyl,-   L₁ may additionally be hydrogen and Z₁, Z₂ and Z₃ may additionally    be hydrogen, hydroxy, mercapto, NO₂, cyano, halogen, formyl,    C₁-C₆alkyl, C₁-C₆haloalkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl,    C₂-C₆alkynyl, C₂-C₆haloalkynyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy,    C₁-C₆alkoxycarbonyl, C₁-C₆alkylcarbonyl, C₁-C₆alkylthio,    C₁-C₆alkylsulfonyl, C₁-C₆alkylsulfinyl, NR₂₂R₂₃, phenyl which may be    mono- or poly-substituted by C₁-C₃alkyl, C₁-C₃haloalkyl,    C₁-C₃alkoxy, C₁-C₃-haloalkoxy, halogen, cyano, hydroxy or nitro, or    C₃-C₆cycloalkyl, C₃-C₆cycloalkyl substituted by C₁-C₃alkoxy,    C₁-C₃alkoxy-C₁-C₃alkyl or C₁-C₃alkyl, 3-oxetanyl, 3-oxetanyl    substituted by C₁-C₃alkoxy, C₁-C₃alkoxy-C₁-C₃alkyl or C₁-C₆alkyl, or    Ar₅, O—Ar₆, N(R₂₄)Ar₇ or S(O)n₆Ar₈.

Preferred compounds of formula I are those wherein p is 0. Preferably atleast one group Z₁, Z₂ or Z₃ is in the ortho-position relative to thecarbonyl group; in preferred compounds, in addition, m₁, m₂ and m₃ arethe number 1. Also preferred are compounds of formula I wherein Q is agroup Q₁ or Q₂, especially the group Q₁.

Also preferred are those compounds of formula I wherein Y is oxygen,NCO₂methyl, NSO₂CH₃, NC(O)CH₃, sulfur, sulfinyl, sulfonyl, C(O) or aC₁-C₂alkylene chain. Outstanding compounds are those wherein Y is aC₁-C₂alkylene chain or oxygen, and wherein A₁ is CR₇, A₂ is CR₈ and R₁,R₂, R₆, R₇, R₈ are each independently of the others hydrogen or methyl,especially Y is methylene or ethylene and R₁, R₂, R₆, R₇, R₈ are eachhydrogen.

Especially interesting compounds of formula I are those wherein Z₁ isC₁-C₃alkylene which may be interrupted by oxygen, especially a bidentategroup of form —CH₂—, —CH₂CH₂—, —OCH₂—, —OCH₂CH₂—, —CH₂O—, —CH₂CH₂O—,—CH₂OCH₂— or —CH₂CH₂CH₂O—, and L₁ is preferably hydrogen, halogen,cyano, C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₂-C₆alkynyl,C₂-C₆haloalkynyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₁-C₆alkoxy-C₁-C₆alkoxy.Especially preferred are compounds of formula I wherein Z₁ or Z₁-L₁ isCH₃, CH₂CH₃, CH₂CH₂CH₃, CHC(CH₃)₂, CH₂OCH₂CH₂OCH₃, CH₂OCH₂CH₂OCH₂CH₃,CH₂OCH₃, CH₂OCH₂CH₃, CH₂OCH(CH₃)₂, CH₂OCH₂CF₃, CH₂OCH₂CH═CH₂,CH₂OCH₂CCH, CH₂OCH₂CCCH₃, CH₂OCH₂CH₂CCH, CH₂OCH₂CN, CH₂OCH₂C₂CN,CH₂OCH₂CH₂CH₂OCH₃, CH₂OCH₂CH₂OCH₂CH₂OCH₃, CH₂OCH₂CH₂CH₂OCF₃, CH₂CH₂OCH₃,CH₂CH₂OCH₂CH₃, CH₂CH₂CH₂OCH₃, CH₂CH₂CH₂OCH₂CH₃ or CH₂CH₂OCH₂CH₂OCH₃,more especially CH₃, CH₂CH₂CH₂OCH₃ or CH₂OCH₂CH₂OCH₃, especiallyprominent compounds being those wherein Y is methylene, ethylene oroxygen, A₁ is CR₇, A₂ is CR₈ and R₁, R₂, R₆, R₇, R₈ are eachindependently of the others hydrogen or methyl. Of that group,preference is given to those compounds wherein Q is Q₁, p₁ is 0 and m₁is 1, the group (Z₁)m₁ is in the ortho-position relative to the carbonylgroup, and R₃ is hydroxy.

Special emphasis should also be given to compounds of formula I whereinQ is Q₁, Z₁ is C₁-C₃alkylene which may be interrupted by oxygen, Z₁being especially a bidentate group of form —CH₂—, —CH₂CH₂—, —OCH₂—,—OCH₂CH₂—, —CH₂O—, —CH₂CH₂O—, —CH₂OCH₂— or —CH₂CH₂CH₂O—, and L₁ ispreferably a monocyclic group

wherein R₂₆ is hydrogen or methyl, R₂₇ is hydrogen, C₁-C₃alkyl,C₁-C₃alkoxy, C₁-C₃alkylthio or trifluoromethyl and X₄ is oxygen orsulfur.

Where no free valency is indicated in those preferred definitions of L₁,for example as in

the linkage site is located at the carbon atom labelled “CH” or in thecase of

at the carbon atom labelled “CH₂” or in a case such as, for example,

at the bonding site indicated at the bottom left.

In a further preferred group of compounds of formula I, X₁, X₂ and X₃are C₁-C₃haloalkyl, especially CF₃, CF₂CF₃, CF₂Cl or CF₂H, moreespecially CF₃ or CF₂H.

An especially preferred group of compounds of formula I comprises thosecompounds wherein

-   Y is oxygen, C(═CR_(6a)R_(6b)) or a C₁-C₄alkylene chain which may be    mono- or poly-substituted by R₆;-   A₁ is CR₇;-   A₂ is CR₈;-   R₁, R₂, R₆, R_(6a), R_(6b), R₇ and R₈ are each independently of the    others hydrogen, C₁-C₆alkyl or C₁-C₆alkoxycarbonyl;-   or two substituents R₆ at the same carbon atom together form a    C₂-C₅alkylene chain;-   R₃ is hydroxy;-   Q is the radical Q₁;-   p₁ is 0;-   m₁ is 1;-   X₁ is C₁-C₆haloalkyl;-   Z₁ is a C₁-C₆alkyl group which is interrupted by oxygen and is mono-    or poly-substituted by L₁; it also being possible for L₁ to be    bonded at the terminal carbon atom of the C₁-C₆alkyl group;-   or Z₁ is C₁-C₆alkyl;-   and L₁ is C₁-C₆alkoxy;-   and agronomically acceptable salts/isomers/enantiomers/tautomers of    those compounds.

The compounds of formula I can be prepared by means of processes knownper se, e.g. as described in WO/0039094, as indicated below withreference to the examples of compounds of formula Ia

wherein R₁, R₂, A₁, A₂, Y, X₁, Z₁, m₁ and p₁ are as defined above.

In a preferred process, for example in the case of compounds of formulaIa

wherein R₁, R₂, A₁, A₂ and Y are as defined above and Q is a group Q₁,

-   a) a compound of formula Q₁a

wherein Z₁, m₁, X₁ and p₁ are as defined above and E₁ is a leavinggroup, for example halogen or cyano, is reacted in an inert organicsolvent, in the presence of a base, with a compound of formula Da

wherein Y, R₁, R₂, A₂ and A₁ are as defined for formula I, to formcompound(s) of formula IIa and/or IIb

and the latter is(are) then isomerised, for example in the presence of abase and a catalytic amount of an acylating agent, for exampledimethylaminopyridine (DMAP), or a cyanide source, e.g. acetonecyanohydrin, potassium cyanide or trimethylsilyl cyanide; or

-   b) a compound of formula Q₁b

wherein Z₁, m₁, p₁ and X₁ are as defined for formula I, is reacted witha compound of formula Da

wherein Y, R₁, R₂, A₁ and A₂ are as defined for formula I, in an inertorganic solvent, in the presence of a base and a coupling reagent, toform compound(s) of formula IIa and/or IIb

and the latter is(are) then isomerised, for example as described underRoute a).

The intermediates of formulae Da, IIa and IIb are novel and have beendeveloped especially for the preparation of the compounds of formula I.The present invention therefore relates also thereto. The novelintermediates of formulae Da, IIa, IIb correspond, in summary, to thegeneral formulae IIIa and IIIb

wherein R₁, R₂, Y, A₁ and A₂ are as defined above and R₂₉ is OH orOC(O)Q wherein Q is as defined for formula I.

The preparation of the compounds of formula I is illustrated in greaterdetail in the following Reaction Schemes.

According to Reaction Scheme 1 it is preferable to prepare the compoundsof formula I having the group Q₁, Q₂ and Q₃ wherein R₃ is hydroxy andp₁, p₂ and p₃ are 0.

Compounds of formula I wherein p₁, p₂ and p₃ are 1, that is to say thecorresponding N-oxides of formula I, can be prepared by reacting acompound of formula I wherein p₁, p₂ and p₃ are 0 with a suitableoxidising agent, for example with the H₂O₂-urea adduct in the presenceof an acid anhydride, e.g. trifluoroacetic anhydride. Such oxidationsare known in the literature, for example from J. Med. Chem., 32 (12),2561-73, 1989 or WO 00/15615.

For the preparation of the compounds of formula I wherein Q is thegroups Q₁, Q₂ and Q₃ and R₃ is hydroxy, for example in accordance withReaction Scheme 1, Route a), the carboxylic acid derivatives of formulaQ₁a wherein E₁ is a leaving group, e.g. halogen, for example iodine,bromine and especially chlorine, N-oxyphthalimide orN,O-dimethylhydroxylamino, or part of an activated ester, e.g.

(formed from dicyclohexylcarbodiimide (DCC) and the correspondingcarboxylic acid) or

(formed from N-ethyl-N′-(3-dimethylaminopropyl)-carbodiimide (EDC) andthe corresponding carboxylic acid) are used as starting materials. Theyare reacted in an inert, organic solvent, e.g. a halogenatedhydrocarbon, for example dichloromethane, a nitrile, for exampleacetonitrile, or an aromatic hydrocarbon, for example toluene, and inthe presence of a base, e.g. an alkylamine, for example triethylamine,an aromatic amine, for example pyridine or 4-dimethylaminopyridine(DMAP), with the dione derivatives of formula Da to form the isomericenol esters of formula IIa or IIb. That esterification can be carriedout at temperatures of from 0° C. to 110° C.

The isomerisation of the enol ester derivatives of formulae IIa and IIbto form the derivatives of formula I wherein R₃ is hydroxy can becarried out, for example, analogously to EP-A-0 353 187, EP-A-0 316 491or WO 97/46530 in the presence of a base. e.g. an alkylamine, forexample triethylamine, a carbonate, for example potassium carbonate, anda catalytic amount of DMAP or a catalytic amount of a cyanide source,for example acetone cyano-hydrin, potassium cyanide or trimethylsilylcyanide. The two reaction steps can be carried out in situ, especiallywhen a cyanide compound of formula Q₁a (E₁=cyano) is used, or in thepresence of a catalytic amount of acetone cyanohydrin or potassiumcyanide, without isolation of the intermediates IIa and IIb.

According to Reaction Scheme 1, Route b), the desired derivatives offormula I wherein R₃ is hydroxy can be obtained e.g. analogously to E.Haslem, Tetrahedron, 2409-2433, 36, 1980 by first preparing enol estersof formula IIa and/or IIb by means of esterification of the carboxylicacids of formula Q₁b with the dione derivatives of formula Da in aninert solvent, for example a halogenated hydrocarbon, for exampledichloromethane, a nitrile, for example acetonitrile, or an aromatichydrocarbon, for example toluene, in the presence of a base, e.g. analkylamine, for example triethylamine, and a coupling agent, for example2-chloro-1-methyl-pyridinium iodide, which enol esters are thenconverted in situ or in a second step into the compounds of formula I.That reaction takes place, depending upon the solvent used, attemperatures of from 0° C. to 110° C. and yields first, as describedunder Route a), the isomeric esters of formulae IIa and IIb, which canbe isomerised to the desired derivatives of formula I (R₃=hydroxy) asdescribed under Route a), for example in the presence of a base and acatalytic amount of DMAP, or a cyanide source, e.g. acetone cyanohydrin.

The activated carboxylic acid derivatives of formula Q₁a in ReactionScheme 1 (Route a) wherein E₁ is a leaving group, e.g. halogen, forexample bromine, iodine or especially chlorine, can be preparedaccording to known standard methods, as described e.g. in C. Ferri“Reaktionen der organischen Synthese”, Georg Thieme Verlag, Stuttgart,1978, page 460 ff. Such reactions are generally known and variousvariations in respect of the leaving group E₁ are described in theliterature.

Compounds of formula I wherein R₃ is other than hydroxy or halogen canbe prepared in accordance with conversion reactions generally known fromthe literature by nucleophilic substitution reactions on chlorides offormula I wherein R₃ is chlorine, which are readily obtainable fromcompounds of formula I wherein R₃ is hydroxy, likewise in accordancewith known processes, by reaction with a chlorinating agent, such asphosgene, thionyl chloride or oxalyl chloride. In such a reaction thereare used, for example, mercaptans, thiophenols or heterocyclic thiols inthe presence of a base, for example 5-ethyl-2-methylpyridine,diisopropyl-ethylamine, triethylamine, sodium hydrogen carbonate, sodiumacetate or potassium carbonate.

Compounds of formula I wherein the substituent R₃ contains thio groupscan be oxidised to the corresponding sulfones and sulfoxides of formulaI analogously to known standard methods, e.g. with peracids, for examplemeta-chloroperbenzoic acid (m-CPBA) or peracetic acid. In that reactionthe degree of oxidation at the sulfur atom (SO— or SO₂—) can becontrolled by the amount of oxidising agent. Other sulfur-containinggroups, for example those in the meanings of R₁, R₂, R₆, R₇, R₈, L₁, X₁,X₂, X₃ or Y, or in alkyl groups and chains interrupted by sulfur, as mayoccur, for example, in Z₁, Z₂ and Z₃, can be oxidised with a suitableoxidising agent, such as m-CPBA or sodium periodate, to thecorresponding sulfone and sulfine (sulfoxido) groups directly incompounds of formula I, as well as in intermediates of formulae IIa,IIb, Da and Db (hereinbelow).

The derivatives of formula I so obtained wherein R₃ is other thanhydroxy can also be in various isomeric forms, which can optionally beisolated in pure form. The invention therefore includes all thosestereoisomeric forms. Examples of those isomeric forms are the followingformulae I′, I″ and I″′, as shown with reference to compounds of formulaI wherein Q is group Q₁.

The compounds of formula Da used as starting materials can be prepared,for example, by treating a compound of formula Db

wherein A₁, A₂, R₁, R₂ and Y are as defined for formula I, Xa ischlorine or bromine and R₃ is hydroxy or C₁-C₆alkoxy, in the presence ofa suitable reducing agent, e.g. tributyltin hydride, or zinc in aceticacid, optionally followed, when R₃ is C₁-C₆alkoxy, by aftertreatment inthe presence of a hydrolysing agent, e.g. dilute hydrochloric acid oraqueous p-toluenesulfonic acid.

Specifically the compounds of formula Db above wherein R₁ and R₂ areeach hydrogen or methyl, A₁ and A₂ are each methylene, Y is oxygen,methylene or ethylene, R₃ is chlorine, bromine or hydroxy and Xa ischlorine or bromine are known from Organic Letters 2002, 4, 1997; Archivder Pharmazie 1987, 320, 1138; J. Amer. Chem. Soc. 1968, 90 2376 andfrom U.S. Pat. No. 3,538,117 and can be prepared in accordance with themethods described therein.

The compounds of formula Da used as starting materials can accordinglyalso be prepared very generally in accordance with those known methods,by reacting a dienophilic compound of formula IV

wherein A₁, A₂, R₁, R₂ and Y are as defined above, in an inert solvent,such as dichloromethane, 1,2-dichloroethane, toluene or chlorobenzene,optionally at elevated temperature or under elevated pressure, in areaction similar to a Diels-Alder reaction, with a tetrahalocyclopropeneof formula V

wherein Xa is chlorine or bromine, and then hydrolysing the resultingbicyclic compound of formula VI

wherein A₁, A₂, R₁, R₂, Xa and Y are as defined above, optionally in thepresence of a suitable catalyst, for example silver nitrate or thesilver tetrafluoroborate salt, or an acid, such as 90-98% sulfuric acid,90% trifluoroacetic acid or p-toluenesulfonic acid, or reacting it withan alcoholate, for example sodium methanolate, potassium ethanolate orlithium isopropanolate, in order thus to obtain a compound of formula Db

wherein A₁, A₂, R₁, R₂, Xa and Y are as defined above, and R₃ dependingupon the reaction conditions is either hydroxy, C₁-C₆alkoxy, chlorine orbromine, which is then further reduced and/or hydrolysed to form a novelcompound of formula Da

wherein A₁, A₂, R₁, R₂ and Y are as defined above.

Compounds of formula VI can thus be reacted further, for example in thepresence of 90-98% sulfuric acid at elevated temperature of about80-100° C., to form compounds of formula Db wherein R₃ is hydroxy and Xais chlorine or bromine, as described in greater detail in J. Amer. Chem.Soc. 1968, 90, 2376.

It is also possible for compounds of formula VI to be converted intocompounds of formula Db wherein R₃ and Xa are both chlorine or bromine,for example in the presence of 90% trifluoroacetic acid at boilingtemperature or in the presence of aqueous silver nitrate at ambienttemperature, as described in Archiv der Pharmazie 1987, 320, 1138 and inOrganic Letters 2002, 4, 1997.

On the other hand, compounds of formula VI can be converted intocompounds of formula Db wherein R₃ is C₁-C₆alkoxy and Xa is chlorine orbromine in good yields at ambient temperature in the presence ofalcoholates of formula R_(3a)O⁻M⁺ wherein R_(3a) is accordinglyC₁-C₆alkyl and M⁺ is an alkali metal salt, in a solvent, such as analcohol R_(3a)OH, toluene or ether, e.g. tetrahydrofuran,dimethoxyethane.

It is also possible for compounds of formula Db wherein Xa is chlorineor bromine and R₃ is hydroxy or C₁-C₆alkoxy to be reduced in thepresence of reducing agents, e.g. tributyltin hydride, in an organicsolvent, such as toluene or tetrahydrofuran, to form compounds offormula Db wherein Xa is hydrogen, as is well known according to generalmethods from the literature for the reduction of a halogen in a positionadjacent to a carbonyl group (see e.g. Comprehensive Org. Funct. Group,Transformations, Vol. 1. ed. S. M. Roberts, Pergamon Press Oxford, 1995,pages 1-11).

Finally, compounds of formula Db wherein R₃ is C₁-C₆alkoxy, chlorine orbromine and Xa is hydrogen can be hydrolysed to compounds of formula Dain the presence of acids, e.g. dilute hydrochloric acid, dilute sulfuricacid or p-toluenesulfonic acid.

The general reaction sequences for the preparation of compounds offormulae Da and Db from compounds of formulae IV and V via intermediatesof formula VI are shown in the following Scheme.

In the reaction of compounds of formula VI and/or Db wherein A₁, A₂, R₁,R₂, Xa and Y are as defined above and R₃ is C₁-C₆alkoxy with alcoholatesof formula R_(3a)O⁻M⁺, it is also possible for compounds of formula VIIto be formed

wherein A₁, A₂, R₁, R₂, Xa and Y are as defined above and R_(3a) isC₁-C₆alkyl or, when glycol is used, two R_(3a) together are —CH₂CH₂—.Those compounds too can be reacted under the reduction conditionsmentioned above, for example with tributyltin hydride or with zinc inthe presence of acetic acid, by way of a compound of formula VIIa

wherein A₁, A₂, R₁, R₂, R_(3a) and Y are as defined above, andsubsequent hydrolysis, for example with dilute hydrochloric acid or acatalytic amount of p-toluenesulfonic acid in water, to form thecompounds of formulae Da and Db

wherein A₁, A₂, R₁, R₂ and Y are as defined above and R₃ is hydroxy andXa is hydrogen, as is shown generally in the following Scheme.

In a further process, compounds of formula Da can also be preparedeither by conversion of a compound of formula VIII

wherein R₁, R₂, A₁, A₂, Y are as defined above and Ra is C₁-C₆alkyl or,when glycol is used, two R_(3a) together are —CH₂CH₂—, by hydrolysis,e.g. by treatment with an aqueous acid, Route c),or by conversion of a compound of formula IX

wherein R₁, R₂, A₁, A₂, Y are as defined above, by means of oxidation,e.g. with selenium dioxide, Route d), first into a diketo compound offormula X

wherein R₁, R₂, A₁, A₂, Y are as defined above, and subsequentconversion of that compound by carbene insertion, e.g. with diazomethaneor with trimethylsilyl-diazomethane, into the 1,3-dione compound Da.

Those processes are also known per se to the person skilled in the art;the compounds can be prepared, depending upon the functionality of thegroups R₁, R₂, A₁, A₂ and Y, by general reaction routes shown in thefollowing Scheme:

Using such routes it is readily possible to obtain, in particular, thosecompounds of formula VIII wherein Y is a C₂alkylene chain substituted byR₆, wherein R₆ is for example alkoxy, benzyloxy, alkylcarbonyl,alkoxycarbonyl, alkylthio or alkylsulfonyl.

Methods of obtaining the starting compounds of formula VII used in theabove-mentioned process are known, for example, from Acc. Chem. Res.2002, 856; J.O.C. 2002, 67, 6493; Organic Letters 2002, 2477; Synlett,2002,1520; Chem. Commun. 2001, 1624; Synlett, 2000, 421; TetrahedronLetters, 1999, 8431; J.O.C. 1999, 64, 4102; J.A.C.S. 1998, 129, 13254;Tetrahedron Letters, 1998, 659; Synlett, 1997, 1351. Methods ofobtaining the starting compounds of formula IX are described, forexample, in Org. Lettr. 2002, 2063; Synthetic Commun. 2001, 707;J.A.C.S. 2001, 123, 1569; Synlett, 1999, 225; Synlett, 1997, 786;Tetrahedron Letters, 1996, 7295; Synthesis, 1995, 845. Compounds offormula X are known, for example, from Synthesis, 2000, 850.

The transformations according to Route d) are likewise known, forexample from Tetr. 1986, 42, 3491. Oxidation is preferably carried outwith selenium dioxide in a solvent, such as acetic acid, at temperaturesof from about 20° C. to about 120° C. and the carbene insertion withdiazomethane is preferably effected at from about −40° C. to about 50°C. in a solvent, such as dichloromethane or diethyl ether. The carbeneinsertion can also be carried out with trimethylsilyldiazomethane, ithaving proved advantageous to work in the presence of a Lewis acidcatalyst, such as boron trifluoride etherate, for example attemperatures of from about −15° C. to about +25° C.

In principle, however, the compounds of formulae Da, Db, VII, VIIa,VIII, IX and X used as starting materials and as intermediates can beprepared, in dependence upon the substituent pattern A₁, A₂, R₁, R₂ andY and also in dependence upon the availability of the startingmaterials, according to any desired methods and reaction routes, therebeing no limitation in respect of the process variants indicated above.

The compounds of formula Da wherein R₁, R₂, A₁, A₂ and Y are as definedabove, and also compounds of formula Db wherein R₁, R₂, A₁, A₂ and Y areas defined above and R₃ is chlorine, bromine, hydroxy or C₁-C₆alkoxy andXa is hydrogen, chlorine or bromine, with the exception of the compounds3-chloro-8-oxa-bicyclo[3.2.1]oct-6-ene-2,4-dione;3-chloro-bicyclo[3.2.1]oct-6-ene-2,4-dione;3-chloro-4-hydroxy-bicyclo[3.2.1]octa-3,6-dien-2-one;3,4-dibromo-8-oxa-bicyclo[3.2.1]octa-3,6-dien-2-one;3,4-dibromo-1,5-dimethyl-8-oxa-bicyclo-[3.2.1]octa-3,6-dien-2-one;3,4-dibromo-bicyclo[3.2.1]octa-3,6-dien-2-one;3,4-dichloro-8-oxa-bicyclo[3.2.1]octa-3,6-dien-2-one;3,4-dichloro-bicyclo[3.2.1]octa-3,6-dien-2-one and7,8-dibromo-5,9-dihydro-5,9-methano-benzocyclohepten-6-one, and also thecompounds of formula VII are novel and constitute valuable intermediatesfor the preparation of compounds of formula I. The present inventionaccordingly relates likewise thereto.

The compounds of formulae Q_(1a), Q_(2a) and Q_(3a) used as startingmaterials and their corresponding acids Q_(1b), Q_(2b) and Q_(3b) areknown from the publications WO 00/15615 and WO 01/94339 or can beprepared in accordance with the methods described therein.

The compounds of formula V used as starting material are likewise known,for example from Synthesis 1987, 260 and from J. Amer. Chem. Soc. 1968,90 2376.

A large number of known standard methods are available for thepreparation of all further compounds of formula I functionalised inaccordance with the definition of A₁, A₂, R₁, R₂, Y and Q, for examplealkylation, halogenation, acylation, amidation, oximation, oxidation andreduction, the choice of a suitable preparation process being governedby the properties (reactivities) of the substituents in question in therespective intermediates of formulae I, Da, Db, VI, VII and VIIa, andespecially the starting materials of formulae IV and V and Q_(1b),Q_(2b) and Q_(3b).

The reactions to form compounds of formula I are advantageously carriedout in aprotic, inert organic solvents. Such solvents are hydrocarbons,such as benzene, toluene, xylene or cyclohexane, chlorinatedhydrocarbons, such as dichloromethane, trichloromethane,tetrachloromethane or chlorobenzene, ethers, such as diethyl ether,ethylene glycol dimethyl ether, diethylene glycol dimethyl ether,tetrahydrofuran or dioxane, nitriles, such as acetonitrile orpropionitrile, amides, such as N,N-dimethylformamide, diethylformamideor N-methylpyrrolidinone. The reaction temperatures are preferably from−20° C. to +120° C. The reactions generally proceed slightlyexothermically and can generally be carried out at room temperature. Inorder to shorten the reaction time or to initiate the reaction, briefheating, up to the boiling point of the reaction mixture, can be carriedout. The reaction times can likewise be shortened by the addition of afew drops of base as reaction catalyst. Suitable bases are especiallytertiary amines, such as trimethylamine, triethylamine, quinuclidine,1,4-diazabicyclo[2.2.2]octane, 1,5-diazabicyclo[4.3.0]non-5-ene or1,5-diazabicyclo[5.4.0]undec-7-ene. It is also possible, however, to useas bases inorganic bases, such as hydrides, e.g. sodium or calciumhydride, hydroxides, e.g. sodium or potassium hydroxide, carbonates,e.g. sodium or potassium carbonate, or hydrogen carbonates, e.g.potassium or sodium hydrogen carbonate. The bases can be used as such oralternatively with catalytic amounts of a phase transfer catalyst, e.g.crown ethers, especially 18-crown-6, or tetraalkylammonium salts.

The end products of formula I can be isolated in conventional manner byconcentration or evaporation of the solvent and purified byrecrystallisation or trituration of the solid residue in solvents inwhich they are not readily soluble, such as ethers, aromatichydrocarbons or chlorinated hydrocarbons, by distillation or by means ofcolumn chromatography or by means of the HPLC technique using a suitableeluant.

The sequence in which the reactions should be carried out in order asfar as possible to avoid secondary reactions will be familiar to theperson skilled in the art. Unless the synthesis is specifically aimed atthe isolation of pure isomers, the product may be obtained in the formof a mixture of two or more isomers, for example chiral centres in thecase of alkyl groups or cis/trans isomerism in the case of alkenylgroups or <E> or <Z> forms. All such isomers can be separated by methodsknown per se, for example chromatography, crystallisation, or producedin the desired form by means of a specific reaction procedure.

For the use according to the invention of the compounds of formula I, orof compositions comprising them, there come into consideration allmethods of application customary in agriculture, for examplepre-emergence application, post-emergence application and seed dressing,and also various methods and techniques such as, for example, thecontrolled release of active ingredient. For that purpose a solution ofthe active ingredient is applied to mineral granule carriers orpolymerised granules (urea/formaldehyde) and dried. If required, it isadditionally possible to apply a coating (coated granules), which allowsthe active ingredient to be released in metered amounts over a specificperiod of time.

The invention therefore relates also to a herbicidal andplant-growth-inhibiting composition comprising a herbicidally effectiveamount of a compound of formula I according to claim 1 on an inertcarrier.

The compounds of formula I can be used as herbicides in unmodified form,that is to say as obtained in the synthesis, but they are preferablyformulated in customary manner together with the adjuvantsconventionally employed in formulation technology e.g. into emulsifiableconcentrates, directly sprayable or dilutable solutions, diluteemulsions, suspensions, mixtures of a suspension and an emulsion(suspoemulsions), wettable powders, soluble powders, dusts, granules ormicrocapsules. Such formulations are described, for example, on pages 9to 13 of WO 97/34485. As with the nature of the compositions, themethods of application, such as spraying, atomising, dusting, wetting,scattering or pouring, are selected in accordance with the intendedobjectives and the prevailing circumstances.

The formulations, that is to say the compositions, preparations ormixtures comprising the compound (active ingredient) of formula I or atleast one compound of formula I and, usually, one or more solid orliquid formulation adjuvants, are prepared in known manner, e.g. byhomogeneously mixing and/or grinding the active ingredients with theformulation adjuvants, for example solvents or solid carriers.Surface-active compounds (surfactants) may also be used in addition inthe preparation of the formulations. Examples of solvents and solidcarriers are given, for example, on page 6 of WO 97/34485.

Depending upon the nature of the compound of formula I to be formulated,suitable surface-active compounds are non-ionic, cationic and/or anionicsurfactants and surfactant mixtures having good emulsifying, dispersingand wetting properties.

Examples of suitable anionic, non-ionic and cationic surfactants arelisted, for example, on pages 7 and 8 of WO 97/34485.

In addition, the surfactants conventionally employed in formulationtechnology, which are described, inter alia, in “McCutcheon's Detergentsand Emulsifiers Annual” MC Publishing Corp., Ridgewood N.J., 1981,Stache, H., “Tensid-Taschenbuch”, Carl Hanser Verlag, Munich/Vienna1981, and M. and J. Ash, “Encyclopedia of Surfactants”, Vol. I-III,Chemical Publishing Co., New York, 1980-81, are also suitable for thepreparation of the herbicidal compositions according to the invention.

The compositions according to the invention can additionally include anadditive comprising an oil of vegetable or animal origin, a mineral oil,alkyl esters thereof or mixtures of such oils and oil derivatives.

The amount of oil additive in the composition according to the inventionis generally from 0.01 to 2%, based on the spray mixture. For example,the oil additive can be added to the spray tank in the desiredconcentration after the spray mixture has been prepared.

Preferred oil additives comprise mineral oils or an oil of vegetableorigin, for example rapeseed oil, olive oil or sunflower oil, emulsifiedvegetable oil, such as AMIGO® obtainable from Rhône-Poulenc Canada Inc.,alkyl esters of oils of vegetable origin, for example the methylderivatives, or an oil of animal origin, such as fish oil or beeftallow. A preferred additive contains as active components essentially80% by weight alkyl esters of fish oils and 15% by weight methylatedrapeseed oil, and also 5% by weight of customary emulsifiers and pHmodifiers.

Especially preferred oil additives comprise alkyl esters of higher fattyacids (C₈-C₂₂), especially the methyl derivatives of C₁₂-C₁₈ fattyacids, for example the methyl esters of lauric acid, palmitic acid andoleic acid. Those esters are known as methyl laurate (CAS-111-82-0),methyl palmitate (CAS-112-39-0) and methyl oleate (CAS-112-62-9). Apreferred fatty acid methyl ester derivative is Emery® 2230 and 2231(Henkel subsidiary Cognis GMBH, DE).

The application and action of the oil additives can be improved bycombining them with surface-active substances, such as non-ionic,anionic or cationic surfactants. Examples of suitable anionic, non-ionicand cationic surfactants are listed on pages 7 and 8 of WO 97/34485.

Preferred surface-active substances are anionic surfactants of thedodecylbenzylsulfonate type, especially the calcium salts thereof, andalso non-ionic surfactants of the fatty alcohol ethoxylate type. Specialpreference is given to ethoxylated C₁₂-C₂₂ fatty alcohols having adegree of ethoxylation of from 5 to 40. Examples of commerciallyavailable, preferred surfactants are the Genapol types (Clariant AG,Muttenz, Switzerland). Also preferred for use as surface-activesubstances are silicone surfactants, especially polyalkyl-oxide-modifiedheptamethyltrisiloxanes, such as are commercially available as e.g.Silwet L-77®, and also perfluorinated surfactants. The concentration ofsurface-active substances in relation to the total additive is generallyfrom 1 to 30% by weight.

Examples of oil additives that consist of mixtures of oils or mineraloils or derivatives thereof with surfactants are Edenor ME SU®,Turbocharge® (Zeneca Agro, Stoney Creek, Ontario, Calif.) and Actipron®(BP Oil UK Limited, GB).

The addition of an organic solvent to the oil additive/surfactantmixture can also bring about a further enhancement of action. Suitablesolvents are, for example, Solvesso® (ESSO) and Aromatic Solvent® (ExxonCorporation) types.

The concentration of such solvents can be from 10 to 80% by weight ofthe total weight.

Such oil additives, which are also described, for example, in U.S. Pat.No. 4,834,908, are suitable for the composition according to theinvention. A commercially available oil additive is known by the nameMERGE®, is obtainable from the BASF Corporation and is essentiallydescribed, for example, in U.S. Pat. No. 4,834,908 in col. 5, as ExampleCOC-1. A further oil additive that is preferred according to theinvention is SCORE® (Novartis Crop Protection Canada.)

In addition to the oil additives listed above, in order to enhance theaction of the compositions according to the invention it is alsopossible for formulations of alkyl pyrrolidones, such as arecommercially available e.g. as Agrimax®, to be added to the spraymixture. Formulations of synthetic latices, such as, for example,polyacrylamide, polyvinyl compounds or poly-1-p-menthene, such as arecommercially available as e.g. Bond®, Courier® or Emerald®, can also beused to enhance action. Solutions that contain propionic acid, forexample Eurogkem Pen-e-trate®, can also be added as action-enhancingagent to the spray mixture.

The herbicidal formulations generally contain from 0.1 to 99% by weight,especially from 0.1 to 95% by weight, of herbicide, from 1 to 99.9% byweight, especially from 5 to 99.8% by weight, of a solid or liquidformulation adjuvant, and from 0 to 25% by weight, especially from 0.1to 25% by weight, of a surfactant. Whereas commercial products willpreferably be formulated as concentrates, the end user will normallyemploy dilute formulations. The compositions may also comprise furtheringredients, such as stabilisers, for example vegetable oils orepoxidised vegetable oils (epoxidised coconut oil, rapeseed oil orsoybean oil), anti-foams, for example silicone oil, preservatives,viscosity regulators, binders, tackifiers, and also fertilisers or otheractive ingredients.

The compounds of formula I are generally applied to the plant or to thelocus thereof at rates of application of from 0.001 to 4 kg/ha,especially from 0.005 to 2 kg/ha. The concentration required to achievethe desired effect can be determined by experiment. It is dependent uponthe nature of the action, the stage of development of the cultivatedplant and of the weed and on the application (place, time, method) andmay vary within wide limits as a function of those parameters.

The compounds of formula I are distinguished by herbicidal andgrowth-inhibiting properties, allowing them to be used in crops ofuseful plants, especially cereals, cotton, soybeans, sugar beet, sugarcane, plantation crops, rape, maize and rice, and also for non-selectiveweed control. The term “crops” is to be understood as including alsocrops that have been rendered tolerant to herbicides or classes ofherbicides (such as, for example, HPPD inhibitors, ALS inhibitors, EPSPS(5-enol-pyrovyl-shikimate-3-phosphate-synthase) inhibitors, GS(glutamine synthetase) inhibitors) as a result of conventional methodsof breeding or genetic engineering. An example of a crop that has beenrendered tolerant to imidazolinones, e.g. imazamox, by conventionalmethods of breeding (mutagenesis) is Clearfield® summer rape (Canola).Examples of crops that have been rendered tolerant to herbicides orclasses of herbicides by genetic engineering methods include glyphosate-and glufosinate-resistant maize varieties commercially available underthe trade names RoundupReady® and LibertyLink®.

Crops are also to be understood as being those which have been renderedresistant to harmful insects by genetic engineering methods, for exampleBt maize (resistant to European corn borer), Bt cotton (resistant tocotton boll weevil) and also Bt potatoes (resistant to the Coloradobeetle). Examples of Bt maize are the Bt 176 maize hybrids of NK®(Syngenta Seeds). The Bt toxin is a protein that is formed naturally byBacillus thuringiensis soil bacteria. Examples of toxins, or transgenicplants able to synthesise such toxins, are described in EP-A-0 451 878,EP-A-0 374 753, WO 93/07278, WO 95/34656 and EP-A-0 427 529.

Plant crops or seed material thereof can be both herbicide-tolerant andat the same time resistant to insect feeding (“stacked” transgenicevents).

The weeds to be controlled may be both monocotyledonous anddicotyledonous weeds, such as, for example, Stellaria, Nasturtium,Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum,Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus,Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida, Xanthium,Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola andVeronica.

The compositions according to the invention may additionally comprisegrowth regulators, for example trinexapac (744), chlormequat chloride(129), clofencet (148), cyclanilide (170), ethephon (281), flurprimidol(355), gibberellic acid (379), inabenfide (421), maleic hydrazide (449),mefluidide (463), mepiquat chloride (465), paclobutrazol (548),prohexadione-calcium (595), uniconazole (746) or thidiazuron (703). Itis also possible for a composition according to the invention tocomprise fungicides, for example azoxystrobin (43), epoxiconazole (48),benomyl (60), bromuconazole (89), bitertanol (77), carbendazim (107),cyproconazole (189), cyprodinil (190), diclomezine (220), difenoconazole(228), diniconazole (247), epoxiconazole (48), ethirimol (284),etridiazole (294), fenarimol (300), fenbuconazole (302), fenpiclonil(311), fenpropidin (313), fenpropimorph (314), ferimzone (321),fludioxonil (334), fluquinconazole (349), flutolanil (360), flutriafol(361), imazalil (410), ipconazole (426), iprodione (428), isoprothiolane(432), kasugamycin (438), kresoxim-methyl (439), spiroxamine (441),mepronil (466), myclobutanil (505), nuarimol (528), pefurazoate (554),pencycuron (556), phthalide (576), probenazole (590), prochloraz (591),propiconazole (607), pyrazophos (619), pyroquilone (633), quinoxyfen(638), quintozene (639), tebuconazole (678), tetraconazole (695),thiabendazole (701), thifluzamide (705), triadimefon (720), triadimenol(721), tricyclazole (734), tridemorph (736), triflumizole (738),triforine (742), triticonazole (745) or vinclozolin (751). The number inbrackets after each active ingredient refers to the entry number of thatactive ingredient in the Pesticide Manual, eleventh ed., British CropProtection Council, 1997.

The following Examples further illustrate the invention but do not limitthe invention.

PREPARATION EXAMPLE 1 Preparation of2,3,4,4-tetrachloro-1,5-dimethyl-8-oxa-bicyclo-[3.2.1]octa-2,6-diene

6.49 g (67.48 mmol) of 2,5-dimethylfuran and 10 g (56.23 mmol) oftetrachlorocyclopropene are heated at boiling temperature in 70 ml oftoluene for 16 hours. The toluene and excess 2,5-dimethylfuran are thenremoved under reduced pressure. The product, 14.77 g (95.9% of theory)of 2,3,4,4-tetrachloro-1,5-dimethyl-8-oxa-bicyclo[3.2.1]octa-2,6-diene,which remains behind in the form of an oil, can be transferred to thenext reaction step without further purification (¹H NMR).

¹H NMR (300 MHz; CDCl₃) δ 6.50 (d, 1H); 6.15 (d, 1H); 1.82 (s, 3H); 1.63(s, 3H).

PREPARATION EXAMPLE P2 Preparation of3,4-dichloro-1,5-dimethyl-8-oxa-bicyclo[3.2.1]octa-3,6-dien-2-one

14 g (51.1 mmol) of unpurified2,3,4,4-tetrachloro-1,5-dimethyl-8-oxa-bicyclo[3.2.1]octa-2,6-diene and17.36 g (102.2 mmol) of silver nitrate are dissolved in 500 ml ofacetone/water 1:1 mixture and heated for 15 hours at a temperature of65-70° C. until the reaction of the reactants is complete (thin-layerchromatography (TLC) monitoring (mobile phase hexane/ethyl acetate4:1)). After the reaction mixture has cooled to ambient temperature,solid sodium hydrogen carbonate is then stirred into the mixture inportions in order to neutralise the nitric acid. The precipitated silverbromide is filtered off and most of the acetone is distilled off underreduced pressure. The aqueous phase that remains behind is extractedthree times with ethyl acetate. The organic extract is washed withwater, dried over sodium sulfate and concentrated by evaporation. Theoily residue is purified by means of silica gel chromatography (eluantgradient: 3-50% ethyl acetate in hexane). 6.1 g (54%) of pure3,4-dichloro-1,5-dimethyl-8-oxa-bicyclo[3.2.1]octa-3,6-dien-2-one areobtained in the form of a pale yellow solid.

¹H NMR (300 MHz; CDCl₃) δ 6.65 (d, 1H); 6.23 (d, 1H); 1.72 (s, 3H); 1.61(s, 3H).

PREPARATION EXAMPLE P3 Preparation of3-chloro-1,5-dimethyl-4-methoxy-8-oxa-bicyclo-[3.2.1]octa-3,6-dien-2-oneand3-chloro-4,4-dimethoxy-1,5-dimethyl-8-oxa-bicyclo[3.2.1]oct-6-en-2-one

6.0 g (27.39 mmol) of3,4-dichloro-1,5-dimethyl-8-oxa-bicyclo[3.2.1]octa-3,6-dien-2-one isintroduced into 39 ml of anhydrous methanol. At a temperature of 0° C.,the reaction mixture is further diluted dropwise with a solution of 15.2ml of 5.4M sodium methanolate (82.17 mmol) and treated with 10 ml ofabsolute methanol. The reaction mixture is then heated to ambienttemperature with 35 minutes' stirring. Using thin-layer chromatography(hexane/ethyl acetate 8:2) it can be established that reaction of thestarting material is complete. The reaction solution is thenconcentrated under reduced pressure. The residue is then extracted bymeans of carbon tetrachloride against water. The aqueous phase isextracted a further three times using fresh carbon tetrachloride. Thecombined organic extracts are dried over sodium sulfate and concentratedby evaporation under reduced pressure; with ice-cooling, the oilyproduct that remains behind crystallises out in the form of a ˜1:1mixture. The mixture is separated by means of column chromatography onsilica gel (eluant: gradient from 1-5% ethyl acetate/hexane). 3.1 g(52.9%) of pure3-chloro-1,5-dimethyl-4-methoxy-8-oxa-bicyclo[3.2.1]octa-3,6-dien-2-oneare isolated.

¹H NMR (300 MHz; CDCl₃) δ 6.48 (d, 1H); 6.24 (d, 1H); 4.24 (s, 3H); 1.60(s, 3H); 1.56 (s, 3H).

A second fraction yields 3.17 g (46.9%) of pure3-chloro-4,4-dimethoxy-1,5-dimethyl-8-oxa-bicyclo[3.2.1]oct-6-en-2-one.

¹H NMR (300 MHz; CDCl₃) δ 6.25 (d, 1H); 6.05 (d, 1H); 5.15 (s, 1H); 3.48(s, 3H); 3.46 (s, 3H); 1.53 (s, 3H); 1.51 (s, 3H).

PREPARATION EXAMPLE P4 Preparation of4,4-dimethoxy-1,5-dimethyl-8-oxa-bicyclo[3.2.1]oct-6-en-2-one

2.2 g (8.92 mmol) of3-chloro-4,4-dimethoxy-1,5-dimethyl-8-oxa-bicyclo[3.2.1]oct-6-en-2-onein 240 ml of toluene are degassed, with heating at reflux temperature,and a catalytic amount of 66 mg of azaisobutyronitrile (AIBN) and asolution of 5.9 ml (22.3 mmol) of tributyltin hydride are added insuccession. The reaction mixture is maintained at reflux temperature fora further 20 minutes to complete the reaction (TLC monitoring:hexane/ethyl acetate 4:1). The reaction mixture is then concentrated byevaporation under reduced pressure. The residue is then taken up inacetonitrile and the tin-containing residues are extracted by means ofhexane. The acetonitrile phase is concentrated by evaporation in vacuo,1.56 g (82.4% of theory) of4,4-dimethoxy-1,5-dimethyl-8-oxa-bicyclo[3.2.1]oct-6-en-2-one remainingbehind in the form of a yellow oil, which can be used for the nextreaction step without further purification.

¹H NMR (300 MHz; CDCl₃) δ 6.22 (d, 1H); 5.90 (d, 1H); 3.41 (s, 3H); 3.25(s, 3H); 2.92 and 2.84 (AB syst., 2H, J=16.5 Hz); 1.55 (s, 3H); 1.45 (s,3H).

PREPARATION EXAMPLE P5 Preparation of1,5-dimethyl-8-oxa-bicyclo[3.2.1]oct-6-ene-2,4-dione

1.61 g (7.59 mmol) of4,4-dimethoxy-1,5-dimethyl-8-oxa-bicyclo[3.2.1]oct-6-en-2-one and 0.432g (2.28 mmol) of p-toluenesulfonic acid are dissolved in a 2:1 mixtureof acetone and water and heated for 50 minutes at a temperature of 70°C. (TLC monitoring: hexane/ethyl acetate 9:1). The acetone is thenremoved under reduced pressure. The aqueous phase is then adjusted to pH9 with saturated sodium hydrogen carbonate solution and extracted threetimes with ethyl acetate to remove neutral components. The aqueous phaseis then adjusted to pH 5 with dilute hydrochloric acid and extractedthree times with fresh ethyl acetate. The organic phase is dried oversodium sulfate and concentrated by evaporation under reduced pressure,there being obtained 1.04 g (82.5%) of technically pure1,5-dimethyl-8-oxa-bicyclo[3.2.1]oct-6-ene-2,4-dione in the form of ayellowish product, which can be used without further purification in thenext reaction step to form compounds of formula I.

¹H NMR (300 MHz; CDCl₃) δ 6.46 (d, 1H); 6.23 (d, 1H); 5.54 (hept., 1H);1.58 (d, 6H); 1.40 (d, 3H); 1.25 (d, 3H).

PREPARATION EXAMPLE P6 Preparation of3-bromo-1,5-dimethyl-4-isopropoxy-8-oxa-bicyclo-[3.2.1]octa-3,6-dien-2-one

A solution of 2.74 g (8.9 mmol) of3,4-dibromo-1,5-dimethyl-8-oxa-bicyclo[3.2.1]octa-3,6-dien-2-one(prepared according to Organic Lett. 4(12), 1997 (2002)) dissolved in 10ml of tetrahydrofuran is added dropwise at ambient temperature to asolution of 5.4 ml (10.7 mmol) of 2M lithium isopropanolate diluted with10 ml of tetrahydrofuran. The mixture is stirred for 3 hours at ambienttemperature until the starting material has reacted completely (TLCmonitoring: hexane/ethyl acetate/hexane 4:1). The reaction solution isthen treated at a temperature of 0° C. with a 10% sodium dihydrogenphosphate solution (20 ml) and water (30 ml) and extracted three timeswith ethyl acetate. Drying over sodium sulfate and concentration byevaporation are carried out. For further purification, the dark oil soobtained is purified by chromatography over silica gel with 5% ethylacetate in hexane. 1.73 g (68% of theory) of pure3-bromo-1,5-dimethyl-4-isopropoxy-8-oxa-bicyclo[3.2.1]octa-3,6-dien-2-oneare isolated.

¹H NMR (300 MHz; CDCl₃) δ 6.46 (d, 1H); 6.23 (d, 1H); 5.54 (hept., 1H);1.58 (d, 6H); 1.40 (d, 3H); 1.25 (d, 3H).

PREPARATION EXAMPLE P7 Preparation of3-bromo-4,4-(1′,2′-ethylenedioxy)-bicyclo[3.2.1]oct-6-en-2-one

A sodium glycolate solution is prepared by stirring 124 mg (5.4 mmol) ofmetallic sodium into 2.7 ml (42.42 mmol) of anhydrous ethylene glycol atambient temperature and, when the sodium has completely dissolved, 1.5ml of tetrahydrofuran are added. To the resulting monosodium glycolatesolution there is then added dropwise a solution of 1 g (3.6 mmol) of3,4-dibromo-bicyclo[3.2.1]octa-3,6-dien-2-one (prepared according toOrganic Lett. 4(12), 1997 (2002)) dissolved in 5 ml of tetrahydrofuran.The reaction mixture is then stirred at ambient temperature for 90minutes with TLC monitoring (mobile phase hexane/ethyl acetate 4:1). Thereaction mixture is then treated with 8 ml of 10% sodium dihydrogenphosphate solution and extracted with ethyl acetate (3×). The organicphase is washed with water to remove ethylene glycol, then dried andconcentrated by evaporation. 930 mg (˜100%) of3-bromo-4,4-ethylenedioxy-bicyclo[3.2.1]oct-6-en-2-one are obtained inthe form of a white solid.

¹H NMR (300 MHz; CDCl₃) δ 6.38 (m, 1H); 6.25 (m, 1H); 5.46 (s, 1H); 4.25(m, 2H); 4.04 (m, 2H); 3.38 (m, 1H); 2.98 (m, 1H); 2.40 (m, 1H); 2.25(m, 1H).

PREPARATION EXAMPLE P8 Preparation of4,4-(1′,2′-ethylenedioxy)-bicyclo[3.2.1]oct-6-en-2-one

A degassed solution of 920 mg (3.55 mmol) of3-bromo-4,4-(1′,2′-ethylenedioxy)-bicyclo-[3.2.1]oct-6-en-2-one in 90 mlof toluene is treated at boiling temperature in succession with acatalytic amount (30 mg) of AIBN and with 2.35 ml (8.88 mmol) oftributyltin hydride. To complete the reaction, the reaction mixture ismaintained at reflux for a further 20 minutes, with TLC monitoring(mobile phase hexane/ethyl acetate 1:1). The reaction mixture is thenconcentrated by evaporation under reduced pressure. The residue is takenup in a small amount of acetonitrile and extracted five times with asmall amount of hexane in order to remove tin-containing secondaryproducts. The acetonitrile phase is then again concentrated byevaporation. 800 mg of4,4-(1′,2′-ethylenedioxy)-bicyclo[3.2.1]oct-6-en-2-one are obtained inthe form of a yellow oil, which can be transferred directly to the nextreaction step without further purification.

¹H NMR (300 MHz; CDCl₃) δ 6.30 (m, 1H); 6.12 (m, 1H); 4.02-3.90 (m,2×2H); 3.10 (m, 1H); 3.06 (d, 1H); 2.83 (m, 1H); 2.45 (d, 1H); 2.40-2.25(m, 2×1H).

PREPARATION EXAMPLE P9 Bicyclo[3.2.1]oct-6-ene-2,4-dione

a) 640 mg (3.55 mmol) of4,4-(1′,2′-ethylenedioxy)-bicyclo[3.2.1]oct-6-en-2-one are heated for 16hours at a temperature of 70° C. in the presence of 200 mg ofp-toluenesulfonic acid in a 2:1 mixture of acetone and water. Afterhydrolysis is complete (TLC monitoring: ethyl acetate/hexane 1:1), theacetone is distilled off under reduced pressure and the aqueous phase isadjusted to pH 9 with saturated sodium hydrogen carbonate solution.After extraction of the aqueous phase three times with ethyl acetate, itis acidified to pH 5 with dilute hydrochloric acid. Extraction iscarried out three times with fresh ethyl acetate, followed by dryingover sodium sulfate and concentration by evaporation in vacuo. 364 mg(75%) of pure bicyclo[3.2.1]oct-6-ene-2,4-dione are obtained in the formof a yellow oil for further reaction to form compounds of formula I.

¹H NMR (300 MHz; CDCl₃) δ 6.22 (m, 2H); 3.50 (d, 1H); 3.45 (m, 2H); 3.22(d, 1H); 2.60-2.45 (m, 2×1H).

b) One-pot process: 100 mg (0.39 mmol) of3-bromo-4,4-(1′,2′-ethylenedioxy)-bicyclo[3.2.1]-oct-6-en-2-one aretaken up in concentrated acetic acid and treated at ambient temperaturewith 80 mg (1.16 mmol) of zinc powder. The progress of the reaction ismonitored by means of thin-layer chromatography (mobile phase:hexane/ethyl acetate 1:1). When after 2 hours brominated startingmaterial can no longer be detected, the reaction mixture is heatedcontinuously at a temperature of 95° C. After a further 2 hours,according to thin-layer chromatography all the reference material4,4-(1′,2′-ethylenedioxy)-bicyclo[3.2.1]oct-6-en-2-one has reacted. Thereaction mixture is filtered and concentrated in vacuo. The residue istreated with saturated sodium hydrogen carbonate solution and extractedthree times with ethyl acetate. The alkaline aqueous phase is adjustedto pH 3-4 with dilute hydrochloric acid and extracted three times withfresh ethyl acetate. After drying of the organic phase over sodiumsulfate and subsequent concentration by evaporation, 45 mg (85% oftheory) of technically pure bicyclo[3.2.1]oct-6-ene-2,4-dione areobtained.

PREPARATION EXAMPLE P10 Preparation of3-[2-(2-methoxy-ethoxymethyl)-6-trifluoromethyl-pyridine-3-carbonyl]-1,5-dimethyl-8-oxa-bicyclo[3.2.1]oct-6-ene-2,4-dione

146 mg (0.879 mmol) of1,5-dimethyl-8-oxa-bicyclo[3.2.1]oct-6-ene-2,4-dione and 245 mg (0.879mmol) of 2-(2-methoxy-ethoxymethyl)-6-trifluoromethyl-nicotinic acid(preparation as described in WO 01/94339) are dissolved in 29 ml ofacetonitrile and treated at ambient temperature with 199 mg (0.966 mmol)of dicyclohexylcarbodiimide. The reaction mixture is stirred for 2 hoursand then 0.184 ml (1.318 mmol) of triethylamine and 0.08 ml (0.879 mmol)of acetone cyanohydrin are added. Stirring is carried out for a further16 hours at ambient temperature, followed by concentration under reducedpressure. The residue that remains behind is chromatographed over silicagel (eluant: toluene/ethanol/dioxane/triethylamine/water 20:8:4:4:1).The product-containing fraction is concentrated. The oily residue isagain dissolved in fresh ethyl acetate and washed with 10 ml of dilutehydrochloric acid (pH 1), and then with water (2×) and sodium chloridesolution (2×). After the solution has been dried over sodium sulfate andconcentrated by evaporation under reduced pressure, 128 mg (34%) of3-[2-(2-methoxy-ethoxymethyl)-6-trifluoromethyl-pyridine-3-carbonyl]-1,5-dimethyl-8-oxa-bicyclo[3.2.1]oct-6-ene-2,4-dioneare obtained in the form of a yellow oil.

¹H NMR (300 MHz; CDCl₃) δ 16.1 (br. s, 1H); 7.68 (m, 2×1H); 6.29 (d,1H); 6.22 (d, 1H); 4.72 (m, 2H); 3.48 (m, 2H); 3.37 (m, 2H); 3.32 (s,3H); 1.68 (s, 3H); 1.48 (s, 3H).

PREPARATION EXAMPLE P11 3-Chloro-bicyclo[3.2.2]non-6-ene-2,4-dione

0.7 g (2.7 mmol) of 2,3,4,4-tetrachloro-bicyclo[3.2.2]nona-2,6-diene(known from U.S. Pat. No. 3,538,117) is heated in a mixture of 1 ml oftrifluoroacetic acid, 4 ml of acetic acid and 1 ml of water for 18 hoursat a temperature of 70° C. The cooled reaction solution is then taken upin diethyl ether and extracted first with water and then with saturatedsodium chloride solution. After chromatographic purification (ethylacetate/hexane 1:4), 0.33 g of3-chloro-bicyclo-[3.2.2]non-6-ene-2,4-dione is obtained as a tautomericmixture of the forms Da and Db.

¹H-NMR (300 MHz; CDCl₃) δ 8.58 (b, 1H); 6.38 (m, 2H); 3.78 (m, 2H); 2.05to 1.80 (m, 4H); tautomeric form Db.

PREPARATION EXAMPLE P12 Bicyclo[3.2.2]non-6ene-2,4-dione

0.19 g (1 mmol) of 3-chloro-bicyclo[3.2.2]non-6-ene-2,4-dione is treatedin the presence of 4 ml of acetic acid with 0.27 g (4 mmol) of zinc andthe mixture is heated for 3 hours at a temperature of 95° C. The cooledreaction mixture is then extracted with ethyl acetate against water andthen washed again with saturated sodium chloride solution. 0.14 g ofamorphous bicyclo[3.2.2]non-6-ene-2,4-dione is obtained as tautomericform Da.

¹H-NMR (300 MHz; CDCl₃) δ 6.22 (m, 2H); 3.58 to 3.51 (m, 2H); 2.12 (m,2H); 1.92 (m, 2H).

PREPARATION EXAMPLE P135-Bromo-7,8-dioxo-bicyclo[2.2.2]oct-5-ene-2-carboxylic acid methyl ester

3 g (9.4 mmol) of5-bromo-8,8-dimethoxy-7-oxo-bicyclo[2.2.2]oct-5-ene-2-carboxylic acidmethyl ester (J.O.C. (202), 67, 6493) are stirred in a mixture of 15 mlof trifluoroacetic acid and 1 ml of water for 12 hours at roomtemperature. Extraction is then carried out with dichloromethane againstwater. The organic phase is dried over sodium sulfate and yields, afterremoval of the solvent, the5-bromo-7,8-dioxo-bicyclo[2.2.2]oct-5-ene-2-carboxylic acid methyl esterin the form of an orange-coloured oil and as a pure isomer.

¹H-NMR (300 MHz; CDCl₃) δ 6.62 (d, 1H); 3.97 (d, 1H); 3.80 (s, 3H); 3.70(m, 1H); 3.20 (d, 1H); 2.63 (m, 1H); 2.40 (m, 1H).

PREPARATION EXAMPLE P148-Bromo-2,4-dioxo-bicyclo[3.2.2]non-8-ene-6-carboxylic acid methyl ester

4.2 ml of trimethylsilyl-diazomethane are added dropwise at atemperature of −10° C. to a solution of 1.91 g (7 mmol) of5-bromo-7,8-dioxo-bicyclo[2.2.2]oct-5-ene-2-carboxylic acid methyl esterin 20 ml of dichloromethane and 0.089 ml (0.7 mmol) of boron trifluorideetherate. The cooling is removed and the reaction mixture is stirred for4 hours at a temperature of 20° C. The reaction solution is thenextracted with water, the organic phase is dried over sodium sulfate andconcentrated by evaporation using a rotary evaporator, and the residueis purified by silica gel chromatography. An isomer of8-bromo-2,4-dioxo-bicyclo[3.2.2]non-8-ene-6-carboxylic acid methyl esteris obtained.

¹H-NMR (300 MHz; CDCl₃) δ 6.42 (d, 1H); 3.86 (d, 1H); 3.75 (d, 1H); 3.68(s, 3H); 3.65 (m, 1H); 3.43 (d, 1H); 3.10 (m, 1H); 2.52 (m, 1H); 2.34(m, 1H); tautomeric form Da.

PREPARATION EXAMPLE P153-(2-Methyl-6-difluoromethyl-pyridine-3-carbonyl)-2,4-dioxo-bicyclo[3.2.2]non-8-ene-6-carboxylicacid methyl ester

Catalytic amounts (10 mg) of azaisobutyronitrile are added to a solutionof 0.10 g (0.24 mmol) of8-bromo-3-(2-methyl-6-difluoromethyl-pyridine-3-carbonyl)-2,4-dioxo-bicyclo-[3.2.2]non-8-ene-6-carboxylicacid methyl ester (Example 1.1155) and 0.149 ml (0.48 mmol) oftris(trimethylsilyl)silane in 3.5 ml of toluene and the reaction mixtureis stirred at a temperature of 80° C. 5 mg portions of freshazaisobutyronitrile dissolved in a small amount of toluene are thenadded four times until, after 6 days, the reaction has come to acomplete standstill (LC-MS monitoring). The solvent is then removedunder reduced pressure and the residue is purified by silica gelchromatography (eluant: gradient mixture of ethylacetate/tetrahydrofuran/hexane and 3% triethylamine). After removal ofthe solvents the triethyl-ammonium salt of3-(2-methyl-6-difluoromethyl-pyridine-3-carbonyl)-2,4-dioxo-bicyclo-[3.2.2]non-8-ene-6-carboxylicacid methyl ester is obtained.

¹H-NMR (300 MHz; CDCl₃) δ 7.30 (m, 2H); 6.51 (t, 1H); 6.35 (m, 1H); 6.18(m, 1H); 3.68 (m, 1H); 3.52 (s, 3H); 3.35 (m, 1H); 3.24 (m, 1H); 3.00(q, 6H); 2.40 (s, 3H); 2.38 (m, 1H); 2.14 (m, 1H); 1.18 (t, 9H).

The following Tables 1 to 3 list preferred compounds of formula I. Thelinkage site of the substituent Z₁ to the pyridine ring is theunsaturated valency; the free bonds represent methyl groups. Forexample, in the group

the —CH₂ group at the nitrogen atom adjacent to the keto group is thelinkage site; the free bond at the nitrogen atom represents methyl. Thatgroup can also be depicted as follows:

TABLE 1 Compounds of formula Ib: (Ib)

No. R₁ R₂ Z₁ R₃₀ X Y p Physical data 1.0000 H H CH₃ H F NSO₂CH₃ 0 1.0001H H CH₃ H Cl NSO₂CH₃ 0 1.0002 H H CH₃ H H NSO₂CH₃ 0 1.0003 H H CH₃ CH₃ FNSO₂CH₃ 0 1.0004 H H CH₃ CH₃ Cl NSO₂CH₃ 0 1.0005 H H CH₃ CH₃ H NSO₂CH₃ 01.0006 H H CH₂CH₃ H F NSO₂CH₃ 0 1.0007 H H CH₂CH₃ H Cl NSO₂CH₃ 0 1.0008H H CH₂CH₃ H H NSO₂CH₃ 0 1.0009 H H CH₂CH₂CH₃ H F NSO₂CH₃ 0 1.0010 H HCH₂CH₂CH₃ H Cl NSO₂CH₃ 0 1.0011 H H CH₂CH₂CH₃ H H NSO₂CH₃ 0 1.0012 H HCH₂OCH₃ H F NSO₂CH₃ 0 1.0013 H H CH₂OCH₃ H Cl NSO₂CH₃ 0 1.0014 H HCH₂OCH₃ H H NSO₂CH₃ 0 1.0015 H H CH₂OCH₂CH₃ H F NSO₂CH₃ 0 1.0016 H HCH₂OCH₂CH₃ H Cl NSO₂CH₃ 0 1.0017 H H CH₂OCH₂CH₃ H H NSO₂CH₃ 0 1.0018 H HCH₂OCH₂CH₂OCH₃ H F NSO₂CH₃ 0 1.0019 H H CH₂OCH₂CH₂OCH₃ H Cl NSO₂CH₃ 01.0020 H H CH₂OCH₂CH₂OCH₃ H H NSO₂CH₃ 0 1.0021 H H CH₂OCH₂CH₂OCH₂CH₃ H FNSO₂CH₃ 0 1.0022 H H CH₂OCH₂CH₂OCH₂CH₃ H Cl NSO₂CH₃ 0 1.0023 H HCH₂OCH₂CH₂OCH₂CH₃ H H NSO₂CH₃ 0 1.0024 H H CH₂CH₂OCH₃ H F NSO₂CH₃ 01.0025 H H CH₂CH₂OCH₃ H Cl NSO₂CH₃ 0 1.0026 H H CH₂CH₂OCH₃ H H NSO₂CH₃ 01.0027 H H CH₂OCH₂C≡CH H F NSO₂CH₃ 0 1.0028 H H CH₂OCH₂C≡CH H Cl NSO₂CH₃0 1.0029 H H CH₂OCH₂C≡CH H H NSO₂CH₃ 0 1.0030 H H CH₂OCH₂C≡CCH₃ H FNSO₂CH₃ 0 1.0031 H H CH₂OCH₂C≡CCH₃ H Cl NSO₂CH₃ 0 1.0032 H HCH₂OCH₂C≡CCH₃ H H NSO₂CH₃ 0 1.0033 H H CH₂CH₂CH₂OCH₃ H F NSO₂CH₃ 01.0034 H H CH₂CH₂CH₂OCH₃ H Cl NSO₂CH₃ 0 1.0035 H H CH₂CH₂CH₂OCH₃ H HNSO₂CH₃ 0 1.0036 H H CH₂OCH₂OCH₃ H F NSO₂CH₃ 0 1.0037 H H CH₂OCH₂OCH₃ HCl NSO₂CH₃ 0 1.0038 H H CH₂OCH₂OCH₃ H H NSO₂CH₃ 0 1.0039 H HCH₂N(CH₃)SO₂CH₃ H F NSO₂CH₃ 0 1.0040 H H CH₂N(CH₃)SO₂CH₃ H Cl NSO₂CH₃ 01.0041 H H CH₂N(CH₃)SO₂CH₃ H H NSO₂CH₃ 0 1.0042 H H CF₃ H F NSO₂CH₃ 01.0043 H H CF₃ H Cl NSO₂CH₃ 0 1.0044 H H CF₃ H H NSO₂CH₃ 0 1.0045 H HCH₂OCH₂CF₃ H F NSO₂CH₃ 0 1.0046 H H CH₂OCH₂CF₃ H Cl NSO₂CH₃ 0 1.0047 H HCH₂OCH₂CF₃ H H NSO₂CH₃ 0 1.0048 H H CH₂OCH₂Ph H F NSO₂CH₃ 0 1.0049 H HCH₂OCH₂Ph H Cl NSO₂CH₃ 0 1.0050 H H CH₂OCH₂Ph H H NSO₂CH₃ 0 1.0051 H HCH₂OCH₂CH═CH₂ H F NSO₂CH₃ 0 1.0052 H H CH₂OCH₂CH═CH₂ H Cl NSO₂CH₃ 01.0053 H H CH₂OCH₂CH═CH₂ H H NSO₂CH₃ 0 1.0054 H H

H F NSO₂CH₃ 0 1.0055 H H

H Cl NSO₂CH₃ 0 1.0056 H H

H H NSO₂CH₃ 0 1.0057 H H

H F NSO₂CH₃ 0 1.0058 H H

H Cl NSO₂CH₃ 0 1.0059 H H

H H NSO₂CH₃ 0 1.0060 H H

H F NSO₂CH₃ 0 1.0061 H H

H Cl NSO₂CH₃ 0 1.0062 H H

H H NSO₂CH₃ 0 1.0063 H H

H F NSO₂CH₃ 0 1.0064 H H

H Cl NSO₂CH₃ 0 1.0065 H H

H H NSO₂CH₃ 0 1.0066 H H

H F NSO₂CH₃ 0 1.0067 H H

H Cl NSO₂CH₃ 0 1.0068 H H

H H NSO₂CH₃ 0 1.0069 H H

H F NSO₂CH₃ 0 1.0070 H H

H Cl NSO₂CH₃ 0 1.0071 H H

H H NSO₂CH₃ 0 1.0072 H H CH₃ H F NSO₂CH₃ 1 1.0073 H H CH₂OCH₃ H FNSO₂CH₃ 1 1.0074 H H CH₂OCH₂CH₂OCH₃ H F NSO₂CH₃ 1 1.0075 H HCH₂CH₂CH₂OCH₃ H F NSO₂CH₃ 1 1.0076 H H CH₂CH₃ H F NSO₂CH₃ 1 1.0077 H HCH₃ H H NSO₂CH₃ 1 1.0078 H H CH₂OCH₃ H H NSO₂CH₃ 1 1.0079 H HCH₂OCH₂CH₂OCH₃ H H NSO₂CH₃ 1 1.0080 H H CH₂CH₂CH₂OCH₃ H H NSO₂CH₃ 11.0081 H H CH₂CH₃ H H NSO₂CH₃ 1 1.0082 CH₃ CH₃ CH₃ H F NSO₂CH₃ 0 1.0083CH₃ CH₃ CH₃ H Cl NSO₂CH₃ 0 1.0084 CH₃ CH₃ CH₃ H H NSO₂CH₃ 0 1.0085 CH₃CH₃ CH₃ CH₃ F NSO₂CH₃ 0 1.0086 CH₃ CH₃ CH₃ CH₃ Cl NSO₂CH₃ 0 1.0087 CH₃CH₃ CH₃ CH₃ H NSO₂CH₃ 0 1.0088 CH₃ CH₃ CH₂CH₃ H F NSO₂CH₃ 0 1.0089 CH₃CH₃ CH₂CH₃ H Cl NSO₂CH₃ 0 1.0090 CH₃ CH₃ CH₂CH₃ H H NSO₂CH₃ 0 1.0091 CH₃CH₃ CH₂CH₂CH₃ H F NSO₂CH₃ 0 1.0092 CH₃ CH₃ CH₂CH₂CH₃ H Cl NSO₂CH₃ 01.0093 CH₃ CH₃ CH₂CH₂CH₃ H H NSO₂CH₃ 0 1.0094 CH₃ CH₃ CH₂OCH₃ H FNSO₂CH₃ 0 1.0095 CH₃ CH₃ CH₂OCH₃ H Cl NSO₂CH₃ 0 1.0096 CH₃ CH₃ CH₂OCH₃ HH NSO₂CH₃ 0 1.0097 CH₃ CH₃ CH₂OCH₂CH₃ H F NSO₂CH₃ 0 1.0098 CH₃ CH₃CH₂OCH₂CH₃ H Cl NSO₂CH₃ 0 1.0099 CH₃ CH₃ CH₂OCH₂CH₃ H H NSO₂CH₃ 0 1.0100CH₃ CH₃ CH₂OCH₂CH₂OCH₃ H F NSO₂CH₃ 0 1.0101 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ H ClNSO₂CH₃ 0 1.0102 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ H H NSO₂CH₃ 0 1.0103 CH₃ CH₃CH₂OCH₂CH₂OCH₂CH₃ H F NSO₂CH₃ 0 1.0104 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ H ClNSO₂CH₃ 0 1.0105 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ H H NSO₂CH₃ 0 1.0106 CH₃ CH₃CH₂CH₂OCH₃ H F NSO₂CH₃ 0 1.0107 CH₃ CH₃ CH₂CH₂OCH₃ H Cl NSO₂CH₃ 0 1.0108CH₃ CH₃ CH₂CH₂OCH₃ H H NSO₂CH₃ 0 1.0109 CH₃ CH₃ CH₂OCH₂C≡CH H F NSO₂CH₃0 1.0110 CH₃ CH₃ CH₂OCH₂C≡CH H Cl NSO₂CH₃ 0 1.0111 CH₃ CH₃ CH₂OCH₂C≡CH HH NSO₂CH₃ 0 1.0112 CH₃ CH₃ CH₂OCH₂C≡CCH₃ H F NSO₂CH₃ 0 1.0113 CH₃ CH₃CH₂OCH₂C≡CCH₃ H Cl NSO₂CH₃ 0 1.0114 CH₃ CH₃ CH₂OCH₂C≡CCH₃ H H NSO₂CH₃ 01.0115 CH₃ CH₃ CH₂CH₂CH₂OCH₃ H F NSO₂CH₃ 0 1.0116 CH₃ CH₃ CH₂CH₂CH₂OCH₃H Cl NSO₂CH₃ 0 1.0117 CH₃ CH₃ CH₂CH₂CH₂OCH₃ H H NSO₂CH₃ 0 1.0118 CH₃ CH₃CH₂OCH₂OCH₃ H F NSO₂CH₃ 0 1.0119 CH₃ CH₃ CH₂OCH₂OCH₃ H Cl NSO₂CH₃ 01.0120 CH₃ CH₃ CH₂OCH₂OCH₃ H H NSO₂CH₃ 0 1.0121 CH₃ CH₃ CH₂N(CH₃)SO₂CH₃H F NSO₂CH₃ 0 1.0122 CH₃ CH₃ CH₂N(CH₃)SO₂CH₃ H Cl NSO₂CH₃ 0 1.0123 CH₃CH₃ CH₂N(CH₃)SO₂CH₃ H H NSO₂CH₃ 0 1.0124 CH₃ CH₃ CF₃ H F NSO₂CH₃ 01.0125 CH₃ CH₃ CF₃ H Cl NSO₂CH₃ 0 1.0126 CH₃ CH₃ CF₃ H H NSO₂CH₃ 01.0127 CH₃ CH₃ CH₂OCH₂CF₃ H F NSO₂CH₃ 0 1.0128 CH₃ CH₃ CH₂OCH₂CF₃ H ClNSO₂CH₃ 0 1.0129 CH₃ CH₃ CH₂OCH₂CF₃ H H NSO₂CH₃ 0 1.0130 CH₃ CH₃CH₂OCH₂Ph H F NSO₂CH₃ 0 1.0131 CH₃ CH₃ CH₂OCH₂Ph H Cl NSO₂CH₃ 0 1.0132CH₃ CH₃ CH₂OCH₂Ph H H NSO₂CH₃ 0 1.0133 CH₃ CH₃ CH₂OCH₂CH═CH₂ H F NSO₂CH₃0 1.0134 CH₃ CH₃ CH₂OCH₂CH═CH₂ H Cl NSO₂CH₃ 0 1.0135 CH₃ CH₃CH₂OCH₂CH═CH₂ H H NSO₂CH₃ 0 1.0136 CH₃ CH₃

H F NSO₂CH₃ 0 1.0137 CH₃ CH₃

H Cl NSO₂CH₃ 0 1.0138 CH₃ CH₃

H H NSO₂CH₃ 0 1.0139 CH₃ CH₃

H F NSO₂CH₃ 0 1.0140 CH₃ CH₃

H Cl NSO₂CH₃ 0 1.0141 CH₃ CH₃

H H NSO₂CH₃ 0 1.0142 CH₃ CH₃

H F NSO₂CH₃ 0 1.0143 CH₃ CH₃

H Cl NSO₂CH₃ 0 1.0144 CH₃ CH₃

H H NSO₂CH₃ 0 1.0145 CH₃ CH₃

H F NSO₂CH₃ 0 1.0146 CH₃ CH₃

H Cl NSO₂CH₃ 0 1.0147 CH₃ CH₃

H H NSO₂CH₃ 0 1.0148 CH₃ CH₃

H F NSO₂CH₃ 0 1.0149 CH₃ CH₃

H Cl NSO₂CH₃ 0 1.0150 CH₃ CH₃

H H NSO₂CH₃ 0 1.0151 CH₃ CH₃

H F NSO₂CH₃ 0 1.0152 CH₃ CH₃

H Cl NSO₂CH₃ 0 1.0153 CH₃ CH₃

H H NSO₂CH₃ 0 1.0154 CH₃ CH₃ CH₃ H F NSO₂CH₃ 1 1.0155 CH₃ CH₃ CH₂OCH₃ HF NSO₂CH₃ 1 1.0156 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ H F NSO₂CH₃ 1 1.0157 CH₃ CH₃CH₂CH₂CH₂OCH₃ H F NSO₂CH₃ I 1.0158 CH₃ CH₃ CH₂CH₃ H F NSO₂CH₃ 1 1.0159CH₃ CH₃ CH₃ H H NSO₂CH₃ 1 1.0160 CH₃ CH₃ CH₂OCH₃ H H NSO₂CH₃ 1 1.0161CH₃ CH₃ CH₂OCH₂CH₂OCH₃ H H NSO₂CH₃ 1 1.0162 CH₃ CH₃ CH₂CH₂CH₂OCH₃ H HNSO₂CH₃ 1 1.0163 CH₃ CH₃ CH₂CH₃ H H NSO₂CH₃ 1 1.0164 H CH₃ CH₃ H FNSO₂CH₃ 0 1.0165 H CH₃ CH₃ H Cl NSO₂CH₃ 0 1.0166 H CH₃ CH₃ H H NSO₂CH₃ 01.0167 H CH₃ CH₃ CH₃ F NSO₂CH₃ 0 1.0168 H CH₃ CH₃ CH₃ Cl NSO₂CH₃ 01.0169 H CH₃ CH₃ CH₃ H NSO₂CH₃ 0 1.0170 H CH₃ CH₂CH₃ H F NSO₂CH₃ 01.0171 H CH₃ CH₂CH₃ H Cl NSO₂CH₃ 0 1.0172 H CH₃ CH₂CH₃ H H NSO₂CH₃ 01.0173 H CH₃ CH₂CH₂CH₃ H F NSO₂CH₃ 0 1.0174 H CH₃ CH₂CH₂CH₃ H Cl NSO₂CH₃0 1.0175 H CH₃ CH₂CH₂CH₃ H H NSO₂CH₃ 0 1.0176 H CH₃ CH₂OCH₃ H F NSO₂CH₃0 1.0177 H CH₃ CH₂OCH₃ H Cl NSO₂CH₃ 0 1.0178 H CH₃ CH₂OCH₃ H H NSO₂CH₃ 01.0179 H CH₃ CH₂OCH₂CH₃ H F NSO₂CH₃ 0 1.0180 H CH₃ CH₂OCH₂CH₃ H ClNSO₂CH₃ 0 1.0181 H CH₃ CH₂OCH₂CH₃ H H NSO₂CH₃ 0 1.0182 H CH₃CH₂OCH₂CH₂OCH₃ H F NSO₂CH₃ 0 1.0183 H CH₃ CH₂OCH₂CH₂OCH₃ H Cl NSO₂CH₃ 01.0184 H CH₃ CH₂OCH₂CH₂OCH₃ H H NSO₂CH₃ 0 1.0185 H CH₃ CH₂OCH₂CH₂OCH₂CH₃H F NSO₂CH₃ 0 1.0186 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ H Cl NSO₂CH₃ 0 1.0187 H CH₃CH₂OCH₂CH₂OCH₂CH₃ H H NSO₂CH₃ 0 1.0188 H CH₃ CH₂CH₂OCH₃ H F NSO₂CH₃ 01.0189 H CH₃ CH₂CH₂OCH₃ H Cl NSO₂CH₃ 0 1.0190 H CH₃ CH₂CH₂OCH₃ H HNSO₂CH₃ 0 1.0191 H CH₃ CH₂OCH₂C≡CH H F NSO₂CH₃ 0 1.0192 H CH₃CH₂OCH₂C≡CH H Cl NSO₂CH₃ 0 1.0193 H CH₃ CH₂OCH₂C≡CH H H NSO₂CH₃ 0 1.0194H CH₃ CH₂OCH₂C≡CCH₃ H F NSO₂CH₃ 0 1.0195 H CH₃ CH₂OCH₂C≡CCH₃ H ClNSO₂CH₃ 0 1.0196 H CH₃ CH₂OCH₂C≡CCH₃ H H NSO₂CH₃ 0 1.0197 H CH₃CH₂CH₂CH₂OCH₃ H F NSO₂CH₃ 0 1.0198 H CH₃ CH₂CH₂CH₂OCH₃ H Cl NSO₂CH₃ 01.0199 H CH₃ CH₂CH₂CH₂OCH₃ H H NSO₂CH₃ 0 1.0200 H CH₃ CH₂OCH₂OCH₃ H FNSO₂CH₃ 0 1.0201 H CH₃ CH₂OCH₂OCH₃ H Cl NSO₂CH₃ 0 1.0202 H CH₃CH₂OCH₂OCH₃ H H NSO₂CH₃ 0 1.0203 H CH₃ CH₂N(CH₃)SO₂CH₃ H F NSO₂CH₃ 01.0204 H CH₃ CH₂N(CH₃)SO₂CH₃ H Cl NSO₂CH₃ 0 1.0205 H CH₃ CH₂N(CH₃)SO₂CH₃H H NSO₂CH₃ 0 1.0206 H CH₃ CF₃ H F NSO₂CH₃ 0 1.0207 H CH₃ CF₃ H ClNSO₂CH₃ 0 1.0208 H CH₃ CF₃ H H NSO₂CH₃ 0 1.0209 H CH₃ CH₂OCH₂CF₃ H FNSO₂CH₃ 0 1.0210 H CH₃ CH₂OCH₂CF₃ H Cl NSO₂CH₃ 0 1.0211 H CH₃ CH₂OCH₂CF₃H H NSO₂CH₃ 0 1.0212 H CH₃ CH₂OCH₂Ph H F NSO₂CH₃ 0 1.0213 H CH₃CH₂OCH₂Ph H Cl NSO₂CH₃ 0 1.0214 H CH₃ CH₂OCH₂Ph H H NSO₂CH₃ 0 1.0215 HCH₃ CH₂OCH₂CH═CH₂ H F NSO₂CH₃ 0 1.0216 H CH₃ CH₂OCH₂CH═CH₂ H Cl NSO₂CH₃0 1.0217 H CH₃ CH₂OCH₂CH═CH₂ H H NSO₂CH₃ 0 1.0218 H CH₃

H F NSO₂CH₃ 0 1.0219 H CH₃

H Cl NSO₂CH₃ 0 1.0220 H CH₃

H H NSO₂CH₃ 0 1.0221 H CH₃

H F NSO₂CH₃ 0 1.0222 H CH₃

H Cl NSO₂CH₃ 0 1.0223 H CH₃

H H NSO₂CH₃ 0 1.0224 H CH₃

H F NSO₂CH₃ 0 1.0225 H CH₃

H Cl NSO₂CH₃ 0 1.0226 H CH₃

H H NSO₂CH₃ 0 1.0227 H CH₃

H F NSO₂CH₃ 0 1.0228 H CH₃

H Cl NSO₂CH₃ 0 1.0229 H CH₃

H H NSO₂CH₃ 0 1.0230 H CH₃

H F NSO₂CH₃ 0 1.0231 H CH₃

H Cl NSO₂CH₃ 0 1.0232 H CH₃

H H NSO₂CH₃ 0 1.0233 H CH₃

H F NSO₂CH₃ 0 1.0234 H CH₃

H Cl NSO₂CH₃ 0 1.0235 H CH₃

H H NSO₂CH₃ 0 1.0236 H CH₃ CH₃ H F NSO₂CH₃ 1 1.0237 H CH₃ CH₂OCH₃ H FNSO₂CH₃ 1 1.0238 H CH₃ CH₂OCH₂CH₂OCH₃ H F NSO₂CH₃ 1 1.0239 H CH₃CH₂CH₂CH₂OCH₃ H F NSO₂CH₃ 1 1.0240 H CH₃ CH₂CH₃ H F NSO₂CH₃ 1 1.0241 HCH₃ CH₃ H H NSO₂CH₃ 1 1.0242 H CH₃ CH₂OCH₃ H H NSO₂CH₃ 1 1.0243 H CH₃CH₂OCH₂CH₂OCH₃ H H NSO₂CH₃ 1 1.0244 H CH₃ CH₂CH₂CH₂OCH₃ H H NSO₂CH₃ 11.0245 H CH₃ CH₂CH₃ H H NSO₂CH₃ 1 1.0246 H H CH₂OCH₂CH₂OCH₃ H F O 01.0247 H H CH₂OCH₂CH₂OCH₃ H Cl O 0 1.0248 H H CH₂OCH₂CH₂OCH₃ H H O 01.0249 H H CH₂OCH₂CH₂OCH₂CH₃ H F O 0 1.0250 H H CH₂OCH₂CH₂OCH₂CH₃ H Cl O0 1.0251 H H CH₂OCH₂CH₂OCH₂CH₃ H H O 0 1.0252 H H CH₂N(CH₃)SO₂CH₃ H F O0 1.0253 H H CH₂N(CH₃)SO₂CH₃ H Cl O 0 1.0254 H H CH₂N(CH₃)SO₂CH₃ H H O 01.0255 H H CH₂OCH₂Ph H F O 0 1.0256 H H CH₂OCH₂Ph H Cl O 0 1.0257 H HCH₂OCH₂Ph H H O 0 1.0258 H H CH₂OCH₂CH₂OH H F O 0 1.0259 H HCH₂OCH₂CH₂OH H Cl O 0 1.0260 H H CH₂OCH₂CH₂OH H H O 0 1.0261 H HCH₂OCH₂CH₂Cl H F O 0 1.0262 H H CH₂OCH₂CH₂Cl H Cl O 0 1.0263 H HCH₂OCH₂CH₂Cl H H O 0 1.0264 H H CH₂OCH₂CF₃ H F O 0 1.0265 H H CH₂OCH₂CF₃H Cl O 0 1.0266 H H CH₂OCH₂CF₃ H H O 0 1.0267 H H CH₂OCH₂CH═CH₂ H F O 01.0268 H H CH₂OCH₂CH═CH₂ H Cl O 0 1.0269 H H CH₂OCH₂CH═CH₂ H H O 01.0270 H H CH₂O(CO)CH₃ H F O 0 1.0271 H H CH₂O(CO)CH₃ H Cl O 0 1.0272 HH CH₂O(CO)CH₃ H H O 0 1.0273 H H CH₂OCH₂C≡CH H F O 0 1.0274 H HCH₂OCH₂C≡CH H Cl O 0 1.0275 H H CH₂OCH₂C≡CH H H O 0 1.0276 H HCH₂OCH₂C≡CCH₃ H F O 0 1.0277 H H CH₂OCH₂C≡CCH₃ H Cl O 0 1.0278 H HCH₂OCH₂C≡CCH₃ H H O 0 1.0279 H H

H F O 0 1.0280 H H

H Cl O 0 1.0281 H H

H H O 0 1.0282 H H

H F O 0 1.0283 H H

H Cl O 0 1.0284 H H

H H O 0 1.0285 H H

H F O 0 1.0286 H H

H Cl O 0 1.0287 H H

H H O 0 1.0288 H H

H F O 0 1.0289 H H

H Cl O 0 1.0290 H H

H H O 0 1.0291 H H

H F O 0 1.0292 H H

H Cl O 0 1.0293 H H

H H O 0 1.0294 H H

H F O 0 1.0295 H H

H Cl O 0 1.0296 H H

H H O 0 1.0297 H H CH₂OCH₂CH₂OCH₃ H F O 1 1.0298 H H CH₂OCH₂CH₂OCH₃ H HO 1 1.0299 H H CH₂OCH₂CH₂OCH₂CH₃ H F O 1 1.0300 H H CH₂OCH₂CH₂OCH₂CH₃ HH O 1 1.0301 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ H F O 0 see Example P10 1.0302 CH₃CH₃ CH₂OCH₂CH₂OCH₃ H Cl O 0 1.0303 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ H H O 0 1.0304CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ H F O 0 1.0305 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ H ClO 0 1.0306 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ H H O 0 1.0307 CH₃ CH₃CH₂N(CH₃)SO₂CH₃ H F O 0 1.0308 CH₃ CH₃ CH₂N(CH₃)SO₂CH₃ H Cl O 0 1.0309CH₃ CH₃ CH₂N(CH₃)SO₂CH₃ H H O 0 1.0310 CH₃ CH₃ CH₂OCH₂Ph H F O 0 1.0311CH₃ CH₃ CH₂OCH₂Ph H Cl O 0 1.0312 CH₃ CH₃ CH₂OCH₂Ph H H O 0 1.0313 CH₃CH₃ CH₂OCH₂CH₂OH H F O 0 1.0314 CH₃ CH₃ CH₂OCH₂CH₂OH H Cl O 0 1.0315 CH₃CH₃ CH₂OCH₂CH₂OH H H O 0 1.0316 CH₃ CH₃ CH₂OCH₂CH₂Cl H F O 0 1.0317 CH₃CH₃ CH₂OCH₂CH₂Cl H Cl O 0 1.0318 CH₃ CH₃ CH₂OCH₂CH₂Cl H H O 0 1.0319 CH₃CH₃ CH₂OCH₂CF₃ H F O 0 1.0320 CH₃ CH₃ CH₂OCH₂CF₃ H Cl O 0 1.0321 CH₃ CH₃CH₂OCH₂CF₃ H H O 0 1.0322 CH₃ CH₃ CH₂OCH₂CH═CH₂ H F O 0 1.0323 CH₃ CH₃CH₂OCH₂CH═CH₂ H Cl O 0 1.0324 CH₃ CH₃ CH₂OCH₂CH═CH₂ H H O 0 1.0325 CH₃CH₃ CH₂O(CO)CH₃ H F O 0 1.0326 CH₃ CH₃ CH₂O(CO)CH₃ H Cl O 0 1.0327 CH₃CH₃ CH₂O(CO)CH₃ H H O 0 1.0328 CH₃ CH₃ CH₂OCH₂C≡CH H F O 0 1.0329 CH₃CH₃ CH₂OCH₂C≡CH H Cl O 0 1.0330 CH₃ CH₃ CH₂OCH₂C≡CH H H O 0 1.0331 CH₃CH₃ CH₂OCH₂C≡CCH₃ H F O 0 1.0332 CH₃ CH₃ CH₂OCH₂C≡CCH₃ H Cl O 0 1.0333CH₃ CH₃ CH₂OCH₂C≡CCH₃ H H O 0 1.0334 CH₃ CH₃

H F O 0 1.0335 CH₃ CH₃

H Cl O 0 1.0336 CH₃ CH₃

H H O 0 1.0337 CH₃ CH₃

H F O 0 1.0338 CH₃ CH₃

H Cl O 0 1.0339 CH₃ CH₃

H H O 0 1.0340 CH₃ CH₃

H F O 0 1.0341 CH₃ CH₃

H Cl O 0 1.0342 CH₃ CH₃

H H O 0 1.0343 CH₃ CH₃

H F O 0 1.0344 CH₃ CH₃

H Cl O 0 1.0345 CH₃ CH₃

H H O 0 1.0346 CH₃ CH₃

H F O 0 1.0347 CH₃ CH₃

H Cl O 0 1.0348 CH₃ CH₃

H H O 0 1.0349 CH₃ CH₃

H F O 0 1.0350 CH₃ CH₃

H Cl O 0 1.0351 CH₃ CH₃

H H O 0 1.0352 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ H F O 1 1.0353 CH₃ CH₃CH₂OCH₂CH₂OCH₃ H H O 1 1.0354 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ H F O 1 1.0355CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ H H O 1 1.0356 H CH₃ CH₂OCH₂CH₂OCH₃ H F O 01.0357 H CH₃ CH₂OCH₂CH₂OCH₃ H Cl O 0 1.0358 H CH₃ CH₂OCH₂CH₂OCH₃ H H O 01.0359 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ H F O 0 1.0360 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ HCl O 0 1.0361 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ H H O 0 1.0362 H CH₃CH₂N(CH₃)SO₂CH₃ H F O 0 1.0363 H CH₃ CH₂N(CH₃)SO₂CH₃ H Cl O 0 1.0364 HCH₃ CH₂N(CH₃)SO₂CH₃ H H O 0 1.0365 H CH₃ CH₂OCH₂Ph H F O 0 1.0366 H CH₃CH₂OCH₂Ph H Cl O 0 1.0367 H CH₃ CH₂OCH₂Ph H H O 0 1.0368 H CH₃CH₂OCH₂CH₂OH H F O 0 1.0369 H CH₃ CH₂OCH₂CH₂OH H Cl O 0 1.0370 H CH₃CH₂OCH₂CH₂OH H H O 0 1.0371 H CH₃ CH₂OCH₂CH₂Cl H F O 0 1.0372 H CH₃CH₂OCH₂CH₂Cl H Cl O 0 1.0373 H CH₃ CH₂OCH₂CH₂Cl H H O 0 1.0374 H CH₃CH₂OCH₂CF₃ H F O 0 1.0375 H CH₃ CH₂OCH₂CF₃ H Cl O 0 1.0376 H CH₃CH₂OCH₂CF₃ H H O 0 1.0377 H CH₃ CH₂OCH₂CH═CH₂ H F O 0 1.0378 H CH₃CH₂OCH₂CH═CH₂ H Cl O 0 1.0379 H CH₃ CH₂OCH₂CH═CH₂ H H O 0 1.0380 H CH₃CH₂O(CO)CH₃ H F O 0 1.0381 H CH₃ CH₂O(CO)CH₃ H Cl O 0 1.0382 H CH₃CH₂O(CO)CH₃ H H O 0 1.0383 H CH₃ CH₂OCH₂C≡CH H F O 0 1.0384 H CH₃CH₂OCH₂C≡CH H Cl O 0 1.0385 H CH₃ CH₂OCH₂C≡CH H H O 0 1.0386 H CH₃CH₂OCH₂C≡CCH₃ H F O 0 1.0387 H CH₃ CH₂OCH₂C≡CCH₃ H Cl O 0 1.0388 H CH₃CH₂OCH₂C≡CCH₃ H H O 0 1.0389 H CH₃

H F O 0 1.0390 H CH₃

H Cl O 0 1.0391 H CH₃

H H O 0 1.0392 H CH₃

H F O 0 1.0393 H CH₃

H Cl O 0 1.0394 H CH₃

H H O 0 1.0395 H CH₃

H F O 0 1.0396 H CH₃

H Cl O 0 1.0397 H CH₃

H H O 0 1.0398 H CH₃

H F O 0 1.0399 H CH₃

H Cl O 0 1.0400 H CH₃

H H O 0 1.0401 H CH₃

H F O 0 1.0402 H CH₃

H Cl O 0 1.0403 H CH₃

H H O 0 1.0404 H CH₃

H F O 0 1.0405 H CH₃

H Cl O 0 1.0406 H CH₃

H H O 0 1.0407 H CH₃ CH₂OCH₂CH₂OCH₃ H F O 1 1.0408 H CH₃ CH₂OCH₂CH₂OCH₃H H O 1 1.0409 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ H F O 1 1.0410 H CH₃CH₂OCH₂CH₂OCH₂CH₃ H H O 1 1.0411 H H CH₂OCH₂CH₂OCH₃ H F CH₂ 0 ¹H NMR(300 MHz; CDCl₃) δ 17.0 (broad s, 1H); 7.62 (s, 2H); 6.47 (m, 1H); 6.35(m, 1H); 4.73 (m, 2H); 3.50 (m, 3H); 3.39 (m, 2H); 3.31 (s, 3H); 3.30(m, 1H); 2.72-2.50 (m, 2H). 1.0412 H H CH₂OCH₂CH₂OCH₃ H Cl CH₂ 0 1.0413H H CH₂OCH₂CH₂OCH₃ H H CH₂ 0 1.0414 H H CH₂OCH₂CH₂OCH₂CH₃ H F CH₂ 01.0415 H H CH₂OCH₂CH₂OCH₂CH₃ H Cl CH₂ 0 1.0416 H H CH₂OCH₂CH₂OCH₂CH₃ H HCH₂ 0 1.0417 H H CH₂N(CH₃)SO₂CH₃ H F CH₂ 0 1.0418 H H CH₂N(CH₃)SO₂CH₃ HCl CH₂ 0 1.0419 H H CH₂N(CH₃)SO₂CH₃ H H CH₂ 0 1.0420 H H CH₂OCH₂Ph H FCH₂ 0 1.0421 H H CH₂OCH₂Ph H Cl CH₂ 0 1.0422 H H CH₂OCH₂Ph H H CH₂ 01.0423 H H CH₂OCH₂CH₂OH H F CH₂ 0 1.0424 H H CH₂OCH₂CH₂OH H Cl CH₂ 01.0425 H H CH₂OCH₂CH₂OH H H CH₂ 0 1.0426 H H CH₂OCH₂CH₂Cl H F CH₂ 01.0427 H H CH₂OCH₂CH₂Cl H Cl CH₂ 0 1.0428 H H CH₂OCH₂CH₂Cl H H CH₂ 01.0429 H H CH₂OCH₂CF₃ H F CH₂ 0 1.0430 H H CH₂OCH₂CF₃ H Cl CH₂ 0 1.0431H H CH₂OCH₂CF₃ H H CH₂ 0 1.0432 H H CH₂OCH₂CH═CH₂ H F CH₂ 0 1.0433 H HCH₂OCH₂CH═CH₂ H Cl CH₂ 0 1.0434 H H CH₂OCH₂CH═CH₂ H H CH₂ 0 1.0435 H HCH₂O(CO)CH₃ H F CH₂ 0 1.0436 H H CH₂O(CO)CH₃ H Cl CH₂ 0 1.0437 H HCH₂O(CO)CH₃ H H CH₂ 0 1.0438 H H CH₂OCH₂C≡CH H F CH₂ 0 1.0439 H HCH₂OCH₂C≡CH H Cl CH₂ 0 1.0440 H H CH₂OCH₂C≡CH H H CH₂ 0 1.0441 H HCH₂OCH₂C≡CCH₃ H F CH₂ 0 1.0442 H H CH₂OCH₂C≡CCH₃ H Cl CH₂ 0 1.0443 H HCH₂OCH₂C≡CCH₃ H H CH₂ 0 1.0444 H H

H F CH₂ 0 1.0445 H H

H Cl CH₂ 0 1.0446 H H

H H CH₂ 0 1.0447 H H

H F CH₂ 0 1.0448 H H

H Cl CH₂ 0 1.0449 H H

H H CH₂ 0 1.0450 H H

H F CH₂ 0 1.0451 H H

H Cl CH₂ 0 1.0452 H H

H H CH₂ 0 1.0453 H H

H F CH₂ 0 1.0454 H H

H Cl CH₂ 0 1.0455 H H

H H CH₂ 0 1.0456 H H

H F CH₂ 0 1.0457 H H

H Cl CH₂ 0 1.0458 H H

H H CH₂ 0 1.0459 H H

H F CH₂ 0 1.0460 H H

H Cl CH₂ 0 1.0461 H H

H H CH₂ 0 1.0462 H H CH₂OCH₂CH₂OCH₃ H F CH₂ 1 1.0463 H H CH₂OCH₂CH₂OCH₃H H CH₂ 1 1.0464 H H CH₂OCH₂CH₂OCH₂CH₃ H F CH₂ 1 1.0465 H HCH₂OCH₂CH₂OCH₂CH₃ H H CH₂ 1 1.0466 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ H F CH₂ 01.0467 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ H Cl CH₂ 0 1.0468 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ HH CH₂ 0 1.0469 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ H F CH₂ 0 1.0470 CH₃ CH₃CH₂OCH₂CH₂OCH₂CH₃ H Cl CH₂ 0 1.0471 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ H H CH₂ 01.0472 CH₃ CH₃ CH₂N(CH₃)SO₂CH₃ H F CH₂ 0 1.0473 CH₃ CH₃ CH₂N(CH₃)SO₂CH₃H Cl CH₂ 0 1.0474 CH₃ CH₃ CH₂N(CH₃)SO₂CH₃ H H CH₂ 0 1.0475 CH₃ CH₃CH₂OCH₂Ph H F CH₂ 0 1.0476 CH₃ CH₃ CH₂OCH₂Ph H Cl CH₂ 0 1.0477 CH₃ CH₃CH₂OCH₂Ph H H CH₂ 0 1.0478 CH₃ CH₃ CH₂OCH₂CH₂OH H F CH₂ 0 1.0479 CH₃ CH₃CH₂OCH₂CH₂OH H Cl CH₂ 0 1.0480 CH₃ CH₃ CH₂OCH₂CH₂OH H H CH₂ 0 1.0481 CH₃CH₃ CH₂OCH₂CH₂Cl H F CH₂ 0 1.0482 CH₃ CH₃ CH₂OCH₂CH₂Cl H Cl CH₂ 0 1.0483CH₃ CH₃ CH₂OCH₂CH₂Cl H H CH₂ 0 1.0484 CH₃ CH₃ CH₂OCH₂CF₃ H F CH₂ 01.0485 CH₃ CH₃ CH₂OCH₂CF₃ H Cl CH₂ 0 1.0486 CH₃ CH₃ CH₂OCH₂CF₃ H H CH₂ 01.0487 CH₃ CH₃ CH₂OCH₂CH═CH₂ H F CH₂ 0 1.0488 CH₃ CH₃ CH₂OCH₂CH═CH₂ H ClCH₂ 0 1.0489 CH₃ CH₃ CH₂OCH₂CH═CH₂ H H CH₂ 0 1.0490 CH₃ CH₃ CH₂O(CO)CH₃H F CH₂ 0 1.0491 CH₃ CH₃ CH₂O(CO)CH₃ H Cl CH₂ 0 1.0492 CH₃ CH₃CH₂O(CO)CH₃ H H CH₂ 0 1.0493 CH₃ CH₃ CH₂OCH₂C≡CH H F CH₂ 0 1.0494 CH₃CH₃ CH₂OCH₂C≡CH H Cl CH₂ 0 1.0495 CH₃ CH₃ CH₂OCH₂C≡CH H H CH₂ 0 1.0496CH₃ CH₃ CH₂OCH₂C≡CCH₃ H F CH₂ 0 1.0497 CH₃ CH₃ CH₂OCH₂C≡CCH₃ H Cl CH₂ 01.0498 CH₃ CH₃ CH₂OCH₂C≡CCH₃ H H CH₂ 0 1.0499 CH₃ CH₃

H F CH₂ 0 1.0500 CH₃ CH₃

H Cl CH₂ 0 1.0501 CH₃ CH₃

H H CH₂ 0 1.0502 CH₃ CH₃

H F CH₂ 0 1.0503 CH₃ CH₃

H Cl CH₂ 0 1.0504 CH₃ CH₃

H H CH₂ 0 1.0505 CH₃ CH₃

H F CH₂ 0 1.0506 CH₃ CH₃

H Cl CH₂ 0 1.0507 CH₃ CH₃

H H CH₂ 0 1.0508 CH₃ CH₃

H F CH₂ 0 1.0509 CH₃ CH₃

H Cl CH₂ 0 1.0510 CH₃ CH₃

H H CH₂ 0 1.0511 CH₃ CH₃

H F CH₂ 0 1.0512 CH₃ CH₃

H Cl CH₂ 0 1.0513 CH₃ CH₃

H H CH₂ 0 1.0514 CH₃ CH₃

H F CH₂ 0 1.0515 CH₃ CH₃

H Cl CH₂ 0 1.0516 CH₃ CH₃

H H CH₂ 0 1.0517 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ H F CH₂ 1 1.0518 CH₃ CH₃CH₂OCH₂CH₂OCH₃ H H CH₂ 1 1.0519 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ H F CH₂ 11.0520 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ H H CH₂ 1 1.0521 H CH₃ CH₂OCH₂CH₂OCH₃ HF CH₂ 0 1.0522 H CH₃ CH₂OCH₂CH₂OCH₃ H Cl CH₂ 0 1.0523 H CH₃CH₂OCH₂CH₂OCH₃ H H CH₂ 0 1.0524 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ H F CH₂ 0 1.0525H CH₃ CH₂OCH₂CH₂OCH₂CH₃ H Cl CH₂ 0 1.0526 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ H HCH₂ 0 1.0527 H CH₃ CH₂N(CH₃)SO₂CH₃ H F CH₂ 0 1.0528 H CH₃CH₂N(CH₃)SO₂CH₃ H Cl CH₂ 0 1.0529 H CH₃ CH₂N(CH₃)SO₂CH₃ H H CH₂ 0 1.0530H CH₃ CH₂OCH₂Ph H F CH₂ 0 1.0531 H CH₃ CH₂OCH₂Ph H Cl CH₂ 0 1.0532 H CH₃CH₂OCH₂Ph H H CH₂ 0 1.0533 H CH₃ CH₂OCH₂CH₂OH H F CH₂ 0 1.0534 H CH₃CH₂OCH₂CH₂OH H Cl CH₂ 0 1.0535 H CH₃ CH₂OCH₂CH₂OH H H CH₂ 0 1.0536 H CH₃CH₂OCH₂CH₂Cl H F CH₂ 0 1.0537 H CH₃ CH₂OCH₂CH₂Cl H Cl CH₂ 0 1.0538 H CH₃CH₂OCH₂CH₂Cl H H CH₂ 0 1.0539 H CH₃ CH₂OCH₂CF₃ H F CH₂ 0 1.0540 H CH₃CH₂OCH₂CF₃ H Cl CH₂ 0 1.0541 H CH₃ CH₂OCH₂CF₃ H H CH₂ 0 1.0542 H CH₃CH₂OCH₂CH═CH₂ H F CH₂ 0 1.0543 H CH₃ CH₂OCH₂CH═CH₂ H Cl CH₂ 0 1.0544 HCH₃ CH₂OCH₂CH═CH₂ H H CH₂ 0 1.0545 H CH₃ CH₂O(CO)CH₃ H F CH₂ 0 1.0546 HCH₃ CH₂O(CO)CH₃ H Cl CH₂ 0 1.0547 H CH₃ CH₂O(CO)CH₃ H H CH₂ 0 1.0548 HCH₃ CH₂OCH₂C≡CH H F CH₂ 0 1.0549 H CH₃ CH₂OCH₂C≡CH H Cl CH₂ 0 1.0550 HCH₃ CH₂OCH₂C≡CH H H CH₂ 0 1.0551 H CH₃ CH₂OCH₂C≡CCH₃ H F CH₂ 0 1.0552 HCH₃ CH₂OCH₂C≡CCH₃ H Cl CH₂ 0 1.0553 H CH₃ CH₂OCH₂C≡CCH₃ H H CH₂ 0 1.0554H CH₃

H F CH₂ 0 1.0555 H CH₃

H Cl CH₂ 0 1.0556 H CH₃

H H CH₂ 0 1.0557 H CH₃

H F CH₂ 0 1.0558 H CH₃

H Cl CH₂ 0 1.0559 H CH₃

H H CH₂ 0 1.0560 H CH₃

H F CH₂ 0 1.0561 H CH₃

H Cl CH₂ 0 1.0562 H CH₃

H H CH₂ 0 1.0563 H CH₃

H F CH₂ 0 1.0564 H CH₃

H Cl CH₂ 0 1.0565 H CH₃

H H CH₂ 0 1.0566 H CH₃

H F CH₂ 0 1.0567 H CH₃

H Cl CH₂ 0 1.0568 H CH₃

H H CH₂ 0 1.0569 H CH₃

H F CH₂ 0 1.0570 H CH₃

H Cl CH₂ 0 1.0571 H CH₃

H H CH₂ 0 1.0572 H CH₃ CH₂OCH₂CH₂OCH₃ H F CH₂ 1 1.0573 H CH₃CH₂OCH₂CH₂OCH₃ H H CH₂ 1 1.0574 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ H F CH₂ 1 1.0575H CH₃ CH₂OCH₂CH₂OCH₂CH₃ H H CH₂ 1 1.0576 H H CH₂OCH₂CH₂OCH₃ H F CH₂CH₂ 0resin 1.0577 H H CH₂OCH₂CH₂OCH₃ H Cl CH₂CH₂ 0 1.0578 H H CH₂OCH₂CH₂OCH₃H H CH₂CH₂ 0 1.0579 H H CH₂OCH₂CH₂OCH₂CH₃ H F CH₂CH₂ 0 1.0580 H HCH₂OCH₂CH₂OCH₂CH₃ H Cl CH₂CH₂ 0 1.0581 H H CH₂OCH₂CH₂OCH₂CH₃ H H CH₂CH₂0 1.0582 H H CH₂N(CH₃)SO₂CH₃ H F CH₂CH₂ 0 1.0583 H H CH₂N(CH₃)SO₂CH₃ HCl CH₂CH₂ 0 1.0584 H H CH₂N(CH₃)SO₂CH₃ H H CH₂CH₂ 0 1.0585 H H CH₂OCH₂PhH F CH₂CH₂ 0 1.0586 H H CH₂OCH₂Ph H Cl CH₂CH₂ 0 1.0587 H H CH₂OCH₂Ph H HCH₂CH₂ 0 1.0588 H H CH₂OCH₂CH₂OH H F CH₂CH₂ 0 1.0589 H H CH₂OCH₂CH₂OH HCl CH₂CH₂ 0 1.0590 H H CH₂OCH₂CH₂OH H H CH₂CH₂ 0 1.0591 H H CH₂OCH₂CH₂ClH F CH₂CH₂ 0 1.0592 H H CH₂OCH₂CH₂Cl H Cl CH₂CH₂ 0 1.0593 H HCH₂OCH₂CH₂Cl H H CH₂CH₂ 0 1.0594 H H CH₂OCH₂CF₃ H F CH₂CH₂ 0 1.0595 H HCH₂OCH₂CF₃ H Cl CH₂CH₂ 0 1.0596 H H CH₂OCH₂CF₃ H H CH₂CH₂ 0 1.0597 H HCH₂OCH₂CH═CH₂ H F CH₂CH₂ 0 1.0598 H H CH₂OCH₂CH═CH₂ H Cl CH₂CH₂ 0 1.0599H H CH₂OCH₂CH═CH₂ H H CH₂CH₂ 0 1.0600 H H CH₂O(CO)CH₃ H F CH₂CH₂ 01.0601 H H CH₂O(CO)CH₃ H Cl CH₂CH₂ 0 1.0602 H H CH₂O(CO)CH₃ H H CH₂CH₂ 01.0603 H H CH₂OCH₂C≡CH H F CH₂CH₂ 0 1.0604 H H CH₂OCH₂C≡CH H Cl CH₂CH₂ 01.0605 H H CH₂OCH₂C≡CH H H CH₂CH₂ 0 1.0606 H H CH₂OCH₂C≡CCH₃ H F CH₂CH₂0 1.0607 H H CH₂OCH₂C≡CCH₃ H Cl CH₂CH₂ 0 1.0608 H H CH₂OCH₂C≡CCH₃ H HCH₂CH₂ 0 1.0609 H H

H F CH₂CH₂ 0 1.0610 H H

H Cl CH₂CH₂ 0 1.0611 H H

H H CH₂CH₂ 0 1.0612 H H

H F CH₂CH₂ 0 1.0613 H H

H Cl CH₂CH₂ 0 1.0614 H H

H H CH₂CH₂ 0 1.0615 H H

H F CH₂CH₂ 0 1.0616 H H

H Cl CH₂CH₂ 0 1.0617 H H

H H CH₂CH₂ 0 1.0618 H H

H F CH₂CH₂ 0 1.0619 H H

H Cl CH₂CH₂ 0 1.0620 H H

H H CH₂CH₂ 0 1.0621 H H

H F CH₂CH₂ 0 1.0622 H H

H Cl CH₂CH₂ 0 1.0623 H H

H H CH₂CH₂ 0 1.0624 H H

H F CH₂CH₂ 0 1.0625 H H

H Cl CH₂CH₂ 0 1.0626 H H

H H CH₂CH₂ 0 1.0627 H H CH₂OCH₂CH₂OCH₃ H F CH₂CH₂ 1 1.0628 H HCH₂OCH₂CH₂OCH₃ H H CH₂CH₂ 1 1.0629 H H CH₂OCH₂CH₂OCH₂CH₃ H F CH₂CH₂ 11.0630 H H CH₂OCH₂CH₂OCH₂CH₃ H H CH₂CH₂ 1 1.0631 CH₃ CH₃ CH₂OCH₂CH₂OCH₃H F CH₂CH₂ 0 1.0632 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ H Cl CH₂CH₂ 0 1.0633 CH₃ CH₃CH₂OCH₂CH₂OCH₃ H H CH₂CH₂ 0 1.0634 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ H F CH₂CH₂0 1.0635 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ H Cl CH₂CH₂ 0 1.0636 CH₃ CH₃CH₂OCH₂CH₂OCH₂CH₃ H H CH₂CH₂ 0 1.0637 CH₃ CH₃ CH₂N(CH₃)SO₂CH₃ H F CH₂CH₂0 1.0638 CH₃ CH₃ CH₂N(CH₃)SO₂CH₃ H Cl CH₂CH₂ 0 1.0639 CH₃ CH₃CH₂N(CH₃)SO₂CH₃ H H CH₂CH₂ 0 1.0640 CH₃ CH₃ CH₂OCH₂Ph H F CH₂CH₂ 01.0641 CH₃ CH₃ CH₂OCH₂Ph H Cl CH₂CH₂ 0 1.0642 CH₃ CH₃ CH₂OCH₂Ph H HCH₂CH₂ 0 1.0643 CH₃ CH₃ CH₂OCH₂CH₂OH H F CH₂CH₂ 0 1.0644 CH₃ CH₃CH₂OCH₂CH₂OH H Cl CH₂CH₂ 0 1.0645 CH₃ CH₃ CH₂OCH₂CH₂OH H H CH₂CH₂ 01.0646 CH₃ CH₃ CH₂OCH₂CH₂Cl H F CH₂CH₂ 0 1.0647 CH₃ CH₃ CH₂OCH₂CH₂Cl HCl CH₂CH₂ 0 1.0648 CH₃ CH₃ CH₂OCH₂CH₂Cl H H CH₂CH₂ 0 1.0649 CH₃ CH₃CH₂OCH₂CF₃ H F CH₂CH₂ 0 1.0650 CH₃ CH₃ CH₂OCH₂CF₃ H Cl CH₂CH₂ 0 1.0651CH₃ CH₃ CH₂OCH₂CF₃ H H CH₂CH₂ 0 1.0652 CH₃ CH₃ CH₂OCH₂CH═CH₂ H F CH₂CH₂0 1.0653 CH₃ CH₃ CH₂OCH₂CH═CH₂ H Cl CH₂CH₂ 0 1.0654 CH₃ CH₃CH₂OCH₂CH═CH₂ H H CH₂CH₂ 0 1.0655 CH₃ CH₃ CH₂O(CO)CH₃ H F CH₂CH₂ 01.0656 CH₃ CH₃ CH₂O(CO)CH₃ H Cl CH₂CH₂ 0 1.0657 CH₃ CH₃ CH₂O(CO)CH₃ H HCH₂CH₂ 0 1.0658 CH₃ CH₃ CH₂OCH₂C≡CH H F CH₂CH₂ 0 1.0659 CH₃ CH₃CH₂OCH₂C≡CH H Cl CH₂CH₂ 0 1.0660 CH₃ CH₃ CH₂OCH₂C≡CH H H CH₂CH₂ 0 1.0661CH₃ CH₃ CH₂OCH₂C≡CCH₃ H F CH₂CH₂ 0 1.0662 CH₃ CH₃ CH₂OCH₂C≡CCH₃ H ClCH₂CH₂ 0 1.0663 CH₃ CH₃ CH₂OCH₂C≡CCH₃ H H CH₂CH₂ 0 1.0664 CH₃ CH₃

H F CH₂CH₂ 0 1.0665 CH₃ CH₃

H Cl CH₂CH₂ 0 1.0666 CH₃ CH₃

H H CH₂CH₂ 0 1.0667 CH₃ CH₃

H F CH₂CH₂ 0 1.0668 CH₃ CH₃

H Cl CH₂CH₂ 0 1.0669 CH₃ CH₃

H H CH₂CH₂ 0 1.0670 CH₃ CH₃

H F CH₂CH₂ 0 1.0671 CH₃ CH₃

H Cl CH₂CH₂ 0 1.0672 CH₃ CH₃

H H CH₂CH₂ 0 1.0673 CH₃ CH₃

H F CH₂CH₂ 0 1.0674 CH₃ CH₃

H Cl CH₂CH₂ 0 1.0675 CH₃ CH₃

H H CH₂CH₂ 0 1.0676 CH₃ CH₃

H F CH₂CH₂ 0 1.0677 CH₃ CH₃

H Cl CH₂CH₂ 0 1.0678 CH₃ CH₃

H H CH₂CH₂ 0 1.0679 CH₃ CH₃

H F CH₂CH₂ 0 1.0680 CH₃ CH₃

H Cl CH₂CH₂ 0 1.0681 CH₃ CH₃

H H CH₂CH₂ 0 1.0682 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ H F CH₂CH₂ 1 1.0683 CH₃ CH₃CH₂OCH₂CH₂OCH₃ H H CH₂CH₂ 1 1.0684 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ H F CH₂CH₂1 1.0685 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ H H CH₂CH₂ 1 1.0686 H CH₃CH₂OCH₂CH₂OCH₃ H F CH₂CH₂ 0 1.0687 H CH₃ CH₂OCH₂CH₂OCH₃ H Cl CH₂CH₂ 01.0688 H CH₃ CH₂OCH₂CH₂OCH₃ H H CH₂CH₂ 0 1.0689 H CH₃ CH₂OCH₂CH₂OCH₂CH₃H F CH₂CH₂ 0 1.0690 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ H Cl CH₂CH₂ 0 1.0691 H CH₃CH₂OCH₂CH₂OCH₂CH₃ H H CH₂CH₂ 0 1.0692 H CH₃ CH₂N(CH₃)SO₂CH₃ H F CH₂CH₂ 01.0693 H CH₃ CH₂N(CH₃)SO₂CH₃ H Cl CH₂CH₂ 0 1.0694 H CH₃ CH₂N(CH₃)SO₂CH₃H H CH₂CH₂ 0 1.0695 H CH₃ CH₂OCH₂Ph H F CH₂CH₂ 0 1.0696 H CH₃ CH₂OCH₂PhH Cl CH₂CH₂ 0 1.0697 H CH₃ CH₂OCH₂Ph H H CH₂CH₂ 0 1.0698 H CH₃CH₂OCH₂CH₂OH H F CH₂CH₂ 0 1.0699 H CH₃ CH₂OCH₂CH₂OH H Cl CH₂CH₂ 0 1.0700H CH₃ CH₂OCH₂CH₂OH H H CH₂CH₂ 0 1.0701 H CH₃ CH₂OCH₂CH₂Cl H F CH₂CH₂ 01.0702 H CH₃ CH₂OCH₂CH₂Cl H Cl CH₂CH₂ 0 1.0703 H CH₃ CH₂OCH₂CH₂Cl H HCH₂CH₂ 0 1.0704 H CH₃ CH₂OCH₂CF₃ H F CH₂CH₂ 0 1.0705 H CH₃ CH₂OCH₂CF₃ HCl CH₂CH₂ 0 1.0706 H CH₃ CH₂OCH₂CF₃ H H CH₂CH₂ 0 1.0707 H CH₃CH₂OCH₂CH═CH₂ H F CH₂CH₂ 0 1.0708 H CH₃ CH₂OCH₂CH═CH₂ H Cl CH₂CH₂ 01.0709 H CH₃ CH₂OCH₂CH═CH₂ H H CH₂CH₂ 0 1.0710 H CH₃ CH₂O(CO)CH₃ H FCH₂CH₂ 0 1.0711 H CH₃ CH₂O(CO)CH₃ H Cl CH₂CH₂ 0 1.0712 H CH₃ CH₂O(CO)CH₃H H CH₂CH₂ 0 1.0713 H CH₃ CH₂OCH₂C≡CH H F CH₂CH₂ 0 1.0714 H CH₃CH₂OCH₂C≡CH H Cl CH₂CH₂ 0 1.0715 H CH₃ CH₂OCH₂C≡CH H H CH₂CH₂ 0 1.0716 HCH₃ CH₂OCH₂C≡CCH₃ H F CH₂CH₂ 0 1.0717 H CH₃ CH₂OCH₂C≡CCH₃ H Cl CH₂CH₂ 01.0718 H CH₃ CH₂OCH₂C≡CCH₃ H H CH₂CH₂ 0 1.0719 H CH₃

H F CH₂CH₂ 0 1.0720 H CH₃

H Cl CH₂CH₂ 0 1.0721 H CH₃

H H CH₂CH₂ 0 1.0722 H CH₃

H F CH₂CH₂ 0 1.0723 H CH₃

H Cl CH₂CH₂ 0 1.0724 H CH₃

H H CH₂CH₂ 0 1.0725 H CH₃

H F CH₂CH₂ 0 1.0726 H CH₃

H Cl CH₂CH₂ 0 1.0727 H CH₃

H H CH₂CH₂ 0 1.0728 H CH₃

H F CH₂CH₂ 0 1.0729 H CH₃

H Cl CH₂CH₂ 0 1.0730 H CH₃

H H CH₂CH₂ Q 1.0731 H CH₃

H F CH₂CH₂ 0 1.0732 H CH₃

H Cl CH₂CH₂ 0 1.0733 H CH₃

H H CH₂CH₂ 0 1.0734 H CH₃

H F CH₂CH₂ 0 1.0735 H CH₃

H Cl CH₂CH₂ 0 1.0736 H CH₃

H H CH₂CH₂ 0 1.0737 H CH₃ CH₂OCH₂CH₂OCH₃ H F CH₂CH₂ 1 1.0738 H CH₃CH₂OCH₂CH₂OCH₃ H H CH₂CH₂ 1 1.0739 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ H F CH₂CH₂ 11.0740 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ H H CH₂CH₂ 1 1.0741 H CH₃ CH₂OCH₂CH₂OCH₃H Cl CH₂CH₂ 1 1.0742 H H CH₂OCH₂CH₂OCH₃ H F NC(O)C(CH₃)₃ 0 1.0743 H HCH₂OCH₂CH₂OCH₃ H Cl NC(O)C(CH₃)₃ 0 1.0744 H H CH₂OCH₂CH₂OCH₃ H HNC(O)C(CH₃)₃ 0 1.0745 H H CH₂OCH₂CH₂OCH₂CH₃ H F NC(O)C(CH₃)₃ 0 1.0746 HH CH₂OCH₂CH₂OCH₂CH₃ H Cl NC(O)C(CH₃)₃ 0 1.0747 H H CH₂OCH₂CH₂OCH₂CH₃ H HNC(O)C(CH₃)₃ 0 1.0748 H H CH₂N(CH₃)SO₂CH₃ H F NC(O)C(CH₃)₃ 0 1.0749 H HCH₂N(CH₃)SO₂CH₃ H Cl NC(O)C(CH₃)₃ 0 1.0750 H H CH₂N(CH₃)SO₂CH₃ H HNC(O)C(CH₃)₃ 0 1.0751 H H CH₂OCH₂Ph H F NC(O)C(CH₃)₃ 0 1.0752 H HCH₂OCH₂Ph H Cl NC(O)C(CH₃)₃ 0 1.0753 H H CH₂OCH₂Ph H H NC(O)C(CH₃)₃ 01.0754 H H CH₂OCH₂CH₂OH H F NC(O)C(CH₃)₃ 0 1.0755 H H CH₂OCH₂CH₂OH H ClNC(O)C(CH₃)₃ 0 1.0756 H H CH₂OCH₂CH₂OH H H NC(O)C(CH₃)₃ 0 1.0757 H HCH₂OCH₂CH₂Cl H F NO(O)O(CH₃)₃ 0 1.0758 H H CH₂OCH₂CH₂Cl H ClNC(O)C(CH₃)₃ 0 1.0759 H H CH₂OCH₂CH₂Cl H H NO(O)C(CH₃)₃ 0 1.0760 H HCH₂OCH₂CF₃ H F NC(O)C(CH₃)₃ 0 1.0761 H H CH₂OCH₂CF₃ H Cl NC(O)C(CH₃)₃ 01.0762 H H CH₂OCH₂CF₃ H H NC(O)C(CH₃)₃ 0 1.0763 H H CH₂OCH₂CH═CH₂ H FNC(O)C(CH₃)₃ 0 1.0764 H H CH₂OCH₂CH═CH₂ H Cl NC(O)C(CH₃)₃ 0 1.0765 H HCH₂OCH₂CH═CH₂ H H NC(O)C(CH₃)₃ 0 1.0766 H H CH₂O(CO)CH₃ H F NC(O)C(CH₃)₃0 1.0767 H H CH₂O(CO)CH₃ H Cl NC(O)C(CH₃)₃ 0 1.0768 H H CH₂O(CO)CH₃ H HNC(O)C(CH₃)₃ 0 1.0769 H H CH₂OCH₂C≡CH H F NC(O)C(CH₃)₃ 0 1.0770 H HCH₂OCH₂C≡CH H Cl NC(O)C(CH₃)₃ 0 1.0771 H H CH₂OCH₂C≡CH H H NC(O)C(CH₃)₃0 1.0772 H H CH₂OCH₂C≡CCH₃ H F NC(O)C(CH₃)₃ 0 1.0773 H H CH₂OCH₂C≡CCH₃ HCl NC(O)C(CH₃)₃ 0 1.0774 H H CH₂OCH₂C≡CCH₃ H H NC(O)C(CH₃)₃ 0 1.0775 H H

H F NC(O)C(CH₃)₃ 0 1.0776 H H

H Cl NC(O)C(CH₃)₃ 0 1.0777 H H

H H NC(O)C(CH₃)₃ 0 1.0778 H H

H F NC(O)C(CH₃)₃ 0 1.0779 H H

H Cl NC(O)C(CH₃)₃ 0 1.0780 H H

H H NC(O)C(CH₃)₃ 0 1.0781 H H

H F NC(O)C(CH₃)₃ 0 1.0782 H H

H Cl NC(O)C(CH₃)₃ 0 1.0783 H H

H H NC(O)C(CH₃)₃ 0 1.0784 H H

H F NC(O)C(CH₃)₃ 0 1.0785 H H

H Cl NC(O)C(CH₃)₃ 0 1.0786 H H

H H NC(O)C(CH₃)₃ 0 1.0787 H H

H F NC(O)C(CH₃)₃ 0 1.0788 H H

H Cl NC(O)C(CH₃)₃ 0 1.0789 H H

H H NC(O)C(CH₃)₃ 0 1.0790 H H

H F NC(O)C(CH₃)₃ 0 1.0791 H H

H Cl NC(O)C(CH₃)₃ 0 1.0792 H H

H H NC(O)C(CH₃)₃ 0 1.0793 H H CH₂OCH₂CH₂OCH₃ H F NC(O)C(CH₃)₃ 1 1.0794 HH CH₂OCH₂CH₂OCH₃ H H NC(O)C(CH₃)₃ 1 1.0795 H H CH₂OCH₂CH₂OCH₂CH₃ H FNC(O)C(CH₃)₃ 1 1.0796 H H CH₂OCH₂CH₂OCH₂CH₃ H H NC(O)C(CH₃)₃ 1 1.0797CH₃ CH₃ CH₂OCH₂CH₂OCH₃ H F NC(O)C(CH₃)₃ 0 1.0798 CH₃ CH₃ CH₂OCH₂CH₂OCH₃H Cl NC(O)C(CH₃)₃ 0 1.0799 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ H H NC(O)C(CH₃)₃ 01.0800 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ H F NC(O)C(CH₃)₃ 0 1.0801 CH₃ CH₃CH₂OCH₂CH₂OCH₂CH₃ H Cl NC(O)C(CH₃)₃ 0 1.0802 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ HH NC(O)C(CH₃)₃ 0 1.0803 CH₃ CH₃ CH₂N(CH₃)SO₂CH₃ H F NC(O)C(CH₃)₃ 01.0804 CH₃ CH₃ CH₂N(CH₃)SO₂CH₃ H Cl NC(O)C(CH₃)₃ 0 1.0805 CH₃ CH₃CH₂N(CH₃)SO₂CH₃ H H NC(O)C(CH₃)₃ 0 1.0806 CH₃ CH₃ CH₂OCH₂Ph H FNC(O)C(CH₃)₃ 0 1.0807 CH₃ CH₃ CH₂OCH₂Ph H Cl NC(O)C(CH₃)₃ 0 1.0808 CH₃CH₃ CH₂OCH₂Ph H H NC(O)C(CH₃)₃ 0 1.0809 CH₃ CH₃ CH₂OCH₂CH₂OH H FNC(O)C(CH₃)₃ 0 1.0810 CH₃ CH₃ CH₂OCH₂CH₂OH H Cl NC(O)C(CH₃)₃ 0 1.0811CH₃ CH₃ CH₂OCH₂CH₂OH H H NC(O)C(CH₃)₃ 0 1.0812 CH₃ CH₃ CH₂OCH₂CH₂Cl H FNC(O)C(CH₃)₃ 0 1.0813 CH₃ CH₃ CH₂OCH₂CH₂Cl H Cl NC(O)C(CH₃)₃ 0 1.0814CH₃ CH₃ CH₂OCH₂CH₂Cl H H NC(O)C(CH₃)₃ 0 1.0815 CH₃ CH₃ CH₂OCH₂CF₃ H FNC(O)C(CH₃)₃ 0 1.0816 CH₃ CH₃ CH₂OCH₂CF₃ H Cl NC(O)C(CH₃)₃ 0 1.0817 CH₃CH₃ CH₂OCH₂CF₃ H H NC(O)C(CH₃)₃ 0 1.0818 CH₃ CH₃ CH₂OCH₂CH═CH₂ H FNC(O)C(CH₃)₃ 0 1.0819 CH₃ CH₃ CH₂OCH₂CH═CH₂ H Cl NC(O)C(CH₃)₃ 0 1.0820CH₃ CH₃ CH₂OCH₂CH═CH₂ H H NC(O)C(CH₃)₃ 0 1.0821 CH₃ CH₃ CH₂O(CO)CH₃ H FNC(O)C(CH₃)₃ 0 1.0822 CH₃ CH₃ CH₂O(CO)CH₃ H Cl NC(O)C(CH₃)₃ 0 1.0823 CH₃CH₃ CH₂O(CO)CH₃ H H NC(O)C(CH₃)₃ 0 1.0824 CH₃ CH₃ CH₂OCH₂C≡CH H FNC(O)C(CH₃)₃ 0 1.0825 CH₃ CH₃ CH₂OCH₂C≡CH H Cl NC(O)C(CH₃)₃ 0 1.0826 CH₃CH₃ CH₂OCH₂C≡CH H H NC(O)C(CH₃)₃ 0 1.0827 CH₃ CH₃ CH₂OCH₂C≡CCH₃ H FNC(O)C(CH₃)₃ 0 1.0828 CH₃ CH₃ CH₂OCH₂C≡CCH₃ H Cl NC(O)C(CH₃)₃ 0 1.0829CH₃ CH₃ CH₂OCH₂C≡CCH₃ H H NC(O)C(CH₃)₃ 0 1.0830 CH₃ CH₃

H F NC(O)C(CH₃)₃ 0 1.0831 CH₃ CH₃

H Cl NC(O)C(CH₃)₃ 0 1.0832 CH₃ CH₃

H H NC(O)C(CH₃)₃ 0 1.0833 CH₃ CH₃

H F NC(O)C(CH₃)₃ 0 1.0834 CH₃ CH₃

H Cl NC(O)C(CH₃)₃ 0 1.0835 CH₃ CH₃

H H NC(O)C(CH₃)₃ 0 1.0836 CH₃ CH₃

H F NC(O)C(CH₃)₃ 0 1.0837 CH₃ CH₃

H Cl NC(O)C(CH₃)₃ 0 1.0838 CH₃ CH₃

H H NC(O)C(CH₃)₃ 0 1.0839 CH₃ CH₃

H F NC(O)C(CH₃)₃ 0 1.0840 CH₃ CH₃

H Cl NC(O)C(CH₃)₃ 0 1.0841 CH₃ CH₃

H H NC(O)C(CH₃)₃ 0 1.0842 CH₃ CH₃

H F NC(O)C(CH₃)₃ 0 1.0843 CH₃ CH₃

H Cl NC(O)C(CH₃)₃ 0 1.0844 CH₃ CH₃

H H NC(O)C(CH₃)₃ 0 1.0845 CH₃ CH₃

H F NC(O)C(CH₃)₃ 0 1.0846 CH₃ CH₃

H Cl NC(O)C(CH₃)₃ 0 1.0847 CH₃ CH₃

H H NC(O)C(CH₃)₃ 0 1.0848 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ H F NC(O)C(CH₃)₃ 11.0849 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ H H NC(O)C(CH₃)₃ 1 1.0850 CH₃ CH₃CH₂OCH₂CH₂OCH₂CH₃ H F NC(O)C(CH₃)₃ 1 1.0851 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ HH NC(O)C(CH₃)₃ 1 1.0852 H CH₃ CH₂OCH₂CH₂OCH₃ H F NC(O)C(CH₃)₃ 0 1.0853 HCH₃ CH₂OCH₂CH₂OCH₃ H Cl NC(O)C(CH₃)₃ 0 1.0854 H CH₃ CH₂OCH₂CH₂OCH₃ H HNC(O)C(CH₃)₃ 0 1.0855 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ H F NC(O)C(CH₃)₃ 0 1.0856H CH₃ CH₂OCH₂CH₂OCH₂CH₃ H Cl NC(O)C(CH₃)₃ 0 1.0857 H CH₃CH₂OCH₂CH₂OCH₂CH₃ H H NC(O)C(CH₃)₃ 0 1.0858 H CH₃ CH₂N(CH₃)SO₂CH₃ H FNC(O)C(CH₃)₃ 0 1.0859 H CH₃ CH₂N(CH₃)SO₂CH₃ H Cl NC(O)C(CH₃)₃ 0 1.0860 HCH₃ CH₂N(CH₃)SO₂CH₃ H H NC(O)C(CH₃)₃ 0 1.0861 H CH₃ CH₂OCH₂Ph H FNC(O)C(CH₃)₃ 0 1.0862 H CH₃ CH₂OCH₂Ph H Cl NC(O)C(CH₃)₃ 0 1.0863 H CH₃CH₂OCH₂Ph H H NC(O)C(CH₃)₃ 0 1.0864 H CH₃ CH₂OCH₂CH₂OH H F NC(O)C(CH₃)₃0 1.0865 H CH₃ CH₂OCH₂CH₂OH H Cl NC(O)C(CH₃)₃ 0 1.0866 H CH₃CH₂OCH₂CH₂OH H H NC(O)C(CH₃)₃ 0 1.0867 H CH₃ CH₂OCH₂CH₂Cl H FNC(O)C(CH₃)₃ 0 1.0868 H CH₃ CH₂OCH₂CH₂Cl H Cl NC(O)C(CH₃)₃ 0 1.0869 HCH₃ CH₂OCH₂CH₂Cl H H NC(O)C(CH₃)₃ 0 1.0870 H CH₃ CH₂OCH₂CF₃ H FNC(O)C(CH₃)₃ 0 1.0871 H CH₃ CH₂OCH₂CF₃ H Cl NC(O)C(CH₃)₃ 0 1.0872 H CH₃CH₂OCH₂CF₃ H H NC(O)C(CH₃)₃ 0 1.0873 H CH₃ CH₂OCH₂CH═CH₂ H FNC(O)C(CH₃)₃ 0 1.0874 H CH₃ CH₂OCH₂CH═CH₂ H Cl NC(O)C(CH₃)₃ 0 1.0875 HCH₃ CH₂OCH₂CH═CH₂ H H NC(O)C(CH₃)₃ 0 1.0876 H CH₃ CH₂O(CO)CH₃ H FNC(O)C(CH₃)₃ 0 1.0877 H CH₃ CH₂O(CO)CH₃ H Cl NC(O)C(CH₃)₃ 0 1.0878 H CH₃CH₂O(CO)CH₃ H H NC(O)C(CH₃)₃ 0 1.0879 H CH₃ CH₂OCH₂C≡CH H F NC(O)C(CH₃)₃0 1.0880 H CH₃ CH₂OCH₂C≡CH H Cl NC(O)C(CH₃)₃ 0 1.0881 H CH₃ CH₂OCH₂C≡CHH H NC(O)C(CH₃)₃ 0 1.0882 H CH₃ CH₂OCH₂C≡CCH₃ H F NC(O)C(CH₃₎ ₃ 0 1.0883H CH₃ CH₂OCH₂C≡CCH₃ H Cl NC(O)C(CH₃)₃ 0 1.0884 H CH₃ CH₂OCH₂C≡CCH₃ H HNC(O)C(CH₃)₃ 0 1.0885 H CH₃

H F NC(O)C(CH₃)₃ 0 1.0886 H CH₃

H Cl NC(O)C(CH₃)₃ 0 1.0887 H CH₃

H H NC(O)C(CH₃)₃ 0 1.0888 H CH₃

H F NC(O)C(CH₃)₃ 0 1.0889 H CH₃

H Cl NC(O)C(CH₃)₃ 0 1.0890 H CH₃

H H NC(O)C(CH₃)₃ 0 1.0891 H CH₃

H F NC(O)C(CH₃)₃ 0 1.0892 H CH₃

H Cl NC(O)C(CH₃)₃ 0 1.0893 H CH₃

H H NC(O)C(CH₃)₃ 0 1.0894 H CH₃

H F NC(O)C(CH₃)₃ 0 1.0895 H CH₃

H Cl NC(O)C(CH₃)₃ 0 1.0896 H CH₃

H H NC(O)C(CH₃)₃ 0 1.0897 H CH₃

H F NC(O)C(CH₃)₃ 0 1.0898 H CH₃

H Cl NC(O)C(CH₃)₃ 0 1.0899 H CH₃

H H NC(O)C(CH₃)₃ 0 1.0900 H CH₃

H F NC(O)C(CH₃)₃ 0 1.0901 H CH₃

H Cl NC(O)C(CH₃)₃ 0 1.0902 H CH₃

H H NC(O)C(CH₃)₃ 0 1.0903 H CH₃ CH₂OCH₂CH₂OCH₃ H F NC(O)C(CH₃)₃ 1 1.0904H CH₃ CH₂OCH₂CH₂OCH₃ H H NC(O)C(CH₃)₃ 1 1.0905 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ HF NC(O)C(CH₃)₃ 1 1.0906 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ H H NC(O)C(CH₃)₃ 11.0907 H H CH₃ H F NSO₂N(CH₃)₂ 0 1.0908 H H CH₃ H Cl NSO₂N(CH₃)₂ 01.0909 H H CH₃ H H NSO₂N(CH₃)₂ 0 1.0910 H H CH₃ CH₃ F NSO₂N(CH₃)₂ 01.0911 H H CH₃ CH₃ Cl NSO₂N(CH₃)₂ 0 1.0912 H H CH₃ CH₃ H NSO₂N(CH₃)₂ 01.0913 H H CH₂CH₃ H F NSO₂N(CH₃)₂ 0 1.0914 H H CH₂CH₃ H Cl NSO₂N(CH₃)₂ 01.0915 H H CH₂CH₃ H H NSO₂N(CH₃)₂ 0 1.0916 H H CH₂CH₂CH₃ H F NSO₂N(CH₃)₂0 1.0917 H H CH₂CH₂CH₃ H Cl NSO₂N(CH₃)₂ 0 1.0918 H H CH₂CH₂CH₃ H HNSO₂N(CH₃)₂ 0 1.0919 H H CH₂OCH₃ H F NSO₂N(CH₃)₂ 0 1.0920 H H CH₂OCH₃ HCl NSO₂N(CH₃)₂ 0 1.0921 H H CH₂OCH₃ H H NSO₂N(CH₃)₂ 0 1.0922 H HCH₂OCH₂CH₃ H F NSO₂N(CH₃)₂ 0 1.0923 H H CH₂OCH₂CH₃ H Cl NSO₂N(CH₃)₂ 01.0924 H H CH₂OCH₂CH₃ H H NSO₂N(CH₃)₂ 0 1.0925 H H CH₂OCH₂CH₂OCH₃ H FNSO₂N(CH₃)₂ 0 1.0926 H H CH₂OCH₂CH₂OCH₃ H Cl NSO₂N(CH₃)₂ 0 1.0927 H HCH₂OCH₂CH₂OCH₃ H H NSO₂N(CH₃)₂ 0 1.0928 H H CH₂OCH₂CH₂OCH₂CH₃ H FNSO₂N(CH₃)₂ 0 1.0929 H H CH₂OCH₂CH₂OCH₂CH₃ H Cl NSO₂N(CH₃)₂ 0 1.0930 H HCH₂OCH₂CH₂OCH₂CH₃ H H NSO₂N(CH₃)₂ 0 1.0931 H H CH₂CH₂OCH₃ H FNSO₂N(CH₃)₂ 0 1.0932 H H CH₂CH₂OCH₃ H Cl NSO₂N(CH₃)₂ 0 1.0933 H HCH₂CH₂OCH₃ H H NSO₂N(CH₃)₂ 0 1.0934 H H CH₂OCH₂C≡CH H F NSO₂N(CH₃)₂ 01.0935 H H CH₂OCH₂C≡CH H Cl NSO₂N(CH₃)₂ 0 1.0936 H H CH₂OCH₂C≡CH H HNSO₂N(CH₃)₂ 0 1.0937 H H CH₂OCH₂C≡CCH₃ H F NSO₂N(CH₃)₂ 0 1.0938 H HCH₂OCH₂C≡CCH₃ H Cl NSO₂N(CH₃)₂ 0 1.0939 H H CH₂OCH₂C≡CCH₃ H HNSO₂N(CH₃)₂ 0 1.0940 H H CH₂CH₂CH₂OCH₃ H F NSO₂N(CH₃)₂ 0 1.0941 H HCH₂CH₂CH₂OCH₃ H Cl NSO₂N(CH₃)₂ 0 1.0942 H H CH₂CH₂CH₂OCH₃ H HNSO₂N(CH₃)₂ 0 1.0943 H H CH₂OCH₂OCH₃ H F NSO₂N(CH₃)₂ 0 1.0944 H HCH₂OCH₂OCH₃ H Cl NSO₂N(CH₃)₂ 0 1.0945 H H CH₂OCH₂OCH₃ H H NSO₂N(CH₃)₂ 01.0946 H H CH₂N(CH₃)SO₂CH₃ H F NSO₂N(CH₃)₂ 0 1.0947 H H CH₂N(CH₃)SO₂CH₃H Cl NSO₂N(CH₃)₂ 0 1.0948 H H CH₂N(CH₃)SO₂CH₃ H H NSO₂N(CH₃)₂ 0 1.0949 HH CF₃ H F NSO₂N(CH₃)₂ 0 1.0950 H H CF₃ H Cl NSO₂N(CH₃)₂ 0 1.0951 H H CF₃H H NSO₂N(CH₃)₂ 0 1.0952 H H CH₂OCH₂CF₃ H F NSO₂N(CH₃)₂ 0 1.0953 H HCH₂OCH₂CF₃ H Cl NSO₂N(CH₃)₂ 0 1.0954 H H CH₂OCH₂CF₃ H H NSO₂N(CH₃)₂ 01.0955 H H CH₂OCH₂Ph H F NSO₂N(CH₃)₂ 0 1.0956 H H CH₂OCH₂Ph H ClNSO₂N(CH₃)₂ 0 1.0957 H H CH₂OCH₂Ph H H NSO₂N(CH₃)₂ 0 1.0958 H HCH₂OCH₂CH═CH₂ H F NSO₂N(CH₃)₂ 0 1.0959 H H CH₂OCH₂CH═CH₂ H ClNSO₂N(CH₃)₂ 0 1.0960 H H CH₂OCH₂CH═CH₂ H H NSO₂N(CH₃)₂ 0 1.0961 H H

H F NSO₂N(CH₃)₂ 0 1.0962 H H

H Cl NSO₂N(CH₃)₂ 0 1.0963 H H

H H NSO₂N(CH₃)₂ 0 1.0964 H H

H F NSO₂N(CH₃)₂ 0 1.0965 H H

H Cl NSO₂N(CH₃)₂ 0 1.0966 H H

H H NSO₂N(CH₃)₂ 0 1.0967 H H

H F NSO₂N(CH₃)₂ 0 1.0968 H H

H Cl NSO₂N(CH₃)₂ 0 1.0969 H H

H H NSO₂N(CH₃)₂ 0 1.0970 H H

H F NSO₂N(CH₃)₂ 0 1.0971 H H

H Cl NSO₂N(CH₃)₂ 0 1.0972 H H

H H NSO₂N(CH₃)₂ 0 1.0973 H H

H F NSO₂N(CH₃)₂ 0 1.0974 H H

H Cl NSO₂N(CH₃)₂ 0 1.0975 H H

H H NSO₂N(CH₃)₂ 0 1.0976 H H

H F NSO₂N(CH₃)₂ 0 1.0977 H H

H Cl NSO₂N(CH₃)₂ 0 1.0978 H H

H H NSO₂N(CH₃)₂ 0 1.0979 H H CH₃ H F NSO₂N(CH₃)₂ 1 1.0980 H H CH₂OCH₃ HF NSO₂N(CH₃)₂ 1 1.0981 H H CH₂OCH₂CH₂OCH₃ H F NSO₂N(CH₃)₂ 1 1.0982 H HCH₂CH₂CH₂OCH₃ H F NSO₂N(CH₃)₂ 1 1.0983 H H CH₂CH₃ H F NSO₂N(CH₃)₂ 11.0984 H H CH₃ H H NSO₂N(CH₃)₂ 1 1.0985 H H CH₂OCH₃ H H NSO₂N(CH₃)₂ 11.0986 H H CH₂OCH₂CH₂OCH₃ H H NSO₂N(CH₃)₂ 1 1.0987 H H CH₂CH₂CH₂OCH₃ H HNSO₂N(CH₃)₂ 1 1.0988 H H CH₂CH₃ H H NSO₂N(CH₃)₂ 1 1.0989 CH₃ CH₃ CH₃ H FNSO₂N(CH₃)₂ 0 1.0990 CH₃ CH₃ CH₃ H Cl NSO₂N(CH₃)₂ 0 1.0991 CH₃ CH₃ CH₃ HH NSO₂N(CH₃)₂ 0 1.0992 CH₃ CH₃ CH₃ CH₃ F NSO₂N(CH₃)₂ 0 1.0993 CH₃ CH₃CH₃ CH₃ Cl NSO₂N(CH₃)₂ 0 1.0994 CH₃ CH₃ CH₃ CH₃ H NSO₂N(CH₃)₂ 0 1.0995CH₃ CH₃ CH₂CH₃ H F NSO₂N(CH₃)₂ 0 1.0996 CH₃ CH₃ CH₂CH₃ H Cl NSO₂N(CH₃)₂0 1.0997 CH₃ CH₃ CH₂CH₃ H H NSO₂N(CH₃)₂ 0 1.0998 CH₃ CH₃ CH₂CH₂CH₃ H FNSO₂N(CH₃)₂ 0 1.0999 CH₃ CH₃ CH₂CH₂CH₃ H Cl NSO₂N(CH₃)₂ 0 1.1000 CH₃ CH₃CH₂CH₂CH₃ H H NSO₂N(CH₃)₂ 0 1.1001 CH₃ CH₃ CH₂OCH₃ H F NSO₂N(CH₃)₂ 01.1002 CH₃ CH₃ CH₂OCH₃ H Cl NSO₂N(CH₃)₂ 0 1.1003 CH₃ CH₃ CH₂OCH₃ H HNSO₂N(CH₃)₂ 0 1.1004 CH₃ CH₃ CH₂OCH₂CH₃ H F NSO₂N(CH₃)₂ 0 1.1005 CH₃ CH₃CH₂OCH₂CH₃ H Cl NSO₂N(CH₃)₂ 0 1.1006 CH₃ CH₃ CH₂OCH₂CH₃ H H NSO₂N(CH₃)₂0 1.1007 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ H F NSO₂N(CH₃)₂ 0 1.1008 CH₃ CH₃CH₂OCH₂CH₂OCH₃ H Cl NSO₂N(CH₃)₂ 0 1.1009 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ H HNSO₂N(CH₃)₂ 0 1.1010 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ H F NSO₂N(CH₃)₂ 0 1.1011CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ H Cl NSO₂N(CH₃)₂ 0 1.1012 CH₃ CH₃CH₂OCH₂CH₂OCH₂CH₃ H H NSO₂N(CH₃)₂ 0 1.1013 CH₃ CH₃ CH₂CH₂OCH₃ H FNSO₂N(CH₃)₂ 0 1.1014 CH₃ CH₃ CH₂CH₂OCH₃ H Cl NSO₂N(CH₃)₂ 0 1.1015 CH₃CH₃ CH₂CH₂OCH₃ H H NSO₂N(CH₃)₂ 0 1.1016 CH₃ CH₃ CH₂OCH₂C≡CH H FNSO₂N(CH₃)₂ 0 1.1017 CH₃ CH₃ CH₂OCH₂C≡CH H Cl NSO₂N(CH₃)₂ 0 1.1018 CH₃CH₃ CH₂OCH₂C≡CH H H NSO₂N(CH₃)₂ 0 1.1019 CH₃ CH₃ CH₂OCH₂C≡CCH₃ H FNSO₂N(CH₃)₂ 0 1.1020 CH₃ CH₃ CH₂OCH₂C≡CCH₃ H Cl NSO₂N(CH₃)₂ 0 1.1021 CH₃CH₃ CH₂OCH₂C≡CCH₃ H H NSO₂N(CH₃)₂ 0 1.1022 CH₃ CH₃ CH₂CH₂CH₂OCH₃ H FNSO₂N(CH₃)₂ 0 1.1023 CH₃ CH₃ CH₂CH₂CH₂OCH₃ H Cl NSO₂N(CH₃)₂ 0 1.1024 CH₃CH₃ CH₂CH₂CH₂OCH₃ H H NSO₂N(CH₃)₂ 0 1.1025 CH₃ CH₃ CH₂OCH₂OCH₃ H FNSO₂N(CH₃)₂ 0 1.1026 CH₃ CH₃ CH₂OCH₂OCH₃ H Cl NSO₂N(CH₃)₂ 0 1.1027 CH₃CH₃ CH₂OCH₂OCH₃ H H NSO₂N(CH₃)₂ 0 1.1028 CH₃ CH₃ CH₂N(CH₃)SO₂CH₃ H FNSO₂N(CH₃)₂ 0 1.1029 CH₃ CH₃ CH₂N(CH₃)SO₂CH₃ H Cl NSO₂N(CH₃)₂ 0 1.1030CH₃ CH₃ CH₂N(CH₃)SO₂CH₃ H H NSO₂N(CH₃)₂ 0 1.1031 CH₃ CH₃ CF₃ H FNSO₂N(CH₃)₂ 0 1.1032 CH₃ CH₃ CF₃ H Cl NSO₂N(CH₃)₂ 0 1.1033 CH₃ CH₃ CF₃ HH NSO₂N(CH₃)₂ 0 1.1034 CH₃ CH₃ CH₂OCH₂CF₃ H F NSO₂N(CH₃)₂ 0 1.1035 CH₃CH₃ CH₂OCH₂CF₃ H Cl NSO₂N(CH₃)₂ 0 1.1036 CH₃ CH₃ CH₂OCH₂CF₃ H HNSO₂N(CH₃)₂ 0 1.1037 CH₃ CH₃ CH₂OCH₂Ph H F NSO₂N(CH₃)₂ 0 1.1038 CH₃ CH₃CH₂OCH₂Ph H Cl NSO₂N(CH₃)₂ 0 1.1039 CH₃ CH₃ CH₂OCH₂Ph H H NSO₂N(CH₃)₂ 01.1040 CH₃ CH₃ CH₂OCH₂CH═CH₂ H F NSO₂N(CH₃)₂ 0 1.1041 CH₃ CH₃CH₂OCH₂CH═CH₂ H Cl NSO₂N(CH₃)₂ 0 1.1042 CH₃ CH₃ CH₂OCH₂CH═CH₂ H HNSO₂N(CH₃)₂ 0 1.1043 CH₃ CH₃

H F NSO₂N(CH₃)₂ 0 1.1044 CH₃ CH₃

H Cl NSO₂N(CH₃)₂ 0 1.1045 CH₃ CH₃

H H NSO₂N(CH₃)₂ 0 1.1046 CH₃ CH₃

H F NSO₂N(CH₃)₂ 0 1.1047 CH₃ CH₃

H Cl NSO₂N(CH₃)₂ 0 1.1048 CH₃ CH₃

H H NSO₂N(CH₃)₂ 0 1.1049 CH₃ CH₃

H F NSO₂N(CH₃)₂ 0 1.1050 CH₃ CH₃

H Cl NSO₂N(CH₃)₂ 0 1.1051 CH₃ CH₃

H H NSO₂N(CH₃)₂ 0 1.1052 CH₃ CH₃

H F NSO₂N(CH₃)₂ 0 1.1053 CH₃ CH₃

H Cl NSO₂N(CH₃)₂ 0 1.1054 CH₃ CH₃

H H NSO₂N(CH₃)₂ 0 1.1055 CH₃ CH₃

H F NSO₂N(CH₃)₂ 0 1.1056 CH₃ CH₃

H Cl NSO₂N(CH₃)₂ 0 1.1057 CH₃ CH₃

H H NSO₂N(CH₃)₂ 0 1.1058 CH₃ CH₃

H F NSO₂N(CH₃)₂ 0 1.1059 CH₃ CH₃

H Cl NSO₂N(CH₃)₂ 0 1.1060 CH₃ CH₃

H H NSO₂N(CH₃)₂ 0 1.1061 CH₃ CH₃ CH₃ H F NSO₂N(CH₃)₂ 1 1.1062 CH₃ CH₃CH₂OCH₃ H F NSO₂N(CH₃)₂ 1 1.1063 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ H F NSO₂N(CH₃)₂1 1.1064 CH₃ CH₃ CH₂CH₂CH₂OCH₃ H F NSO₂N(CH₃)₂ 1 1.1065 CH₃ CH₃ CH₂CH₃ HF NSO₂N(CH₃)₂ 1 1.1066 CH₃ CH₃ CH₃ H H NSO₂N(CH₃)₂ 1 1.1067 CH₃ CH₃CH₂OCH₃ H H NSO₂N(CH₃)₂ 1 1.1068 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ H H NSO₂N(CH₃)₂1 1.1069 CH₃ CH₃ CH₂CH₂CH₂OCH₃ H H NSO₂N(CH₃)₂ 1 1.1070 CH₃ CH₃ CH₂CH₃ HH NSO₂N(CH₃)₂ 1 1.1071 H CH₃ CH₃ H F NSO₂N(CH₃)₂ 0 1.1072 H CH₃ CH₃ H ClNSO₂N(CH₃)₂ 0 1.1073 H CH₃ CH₃ H H NSO₂N(CH₃)₂ 0 1.1074 H CH₃ CH₃ CH₃ FNSO₂N(CH₃)₂ 0 1.1075 H CH₃ CH₃ CH₃ Cl NSO₂N(CH₃)₂ 0 1.1076 H CH₃ CH₃ CH₃H NSO₂N(CH₃)₂ 0 1.1077 H CH₃ CH₂CH₃ H F NSO₂N(CH₃)₂ 0 1.1078 H CH₃CH₂CH₃ H Cl NSO₂N(CH₃)₂ 0 1.1079 H CH₃ CH₂CH₃ H H NSO₂N(CH₃)₂ 0 1.1080 HCH₃ CH₂CH₂CH₃ H F NSO₂N(CH₃)₂ 0 1.1081 H CH₃ CH₂CH₂CH₃ H Cl NSO₂N(CH₃)₂0 1.1082 H CH₃ CH₂CH₂CH₃ H H NSO₂N(CH₃)₂ 0 1.1083 H CH₃ CH₂OCH₃ H FNSO₂N(CH₃)₂ 0 1.1084 H CH₃ CH₂OCH₃ H Cl NSO₂N(CH₃)₂ 0 1.1085 H CH₃CH₂OCH₃ H H NSO₂N(CH₃)₂ 0 1.1086 H CH₃ CH₂OCH₂CH₃ H F NSO₂N(CH₃)₂ 01.1087 H CH₃ CH₂OCH₂CH₃ H Cl NSO₂N(CH₃)₂ 0 1.1088 H CH₃ CH₂OCH₂CH₃ H HNSO₂N(CH₃)₂ 0 1.1089 H CH₃ CH₂OCH₂CH₂OCH₃ H F NSO₂N(CH₃)₂ 0 1.1090 H CH₃CH₂OCH₂CH₂OCH₃ H Cl NSO₂N(CH₃)₂ 0 1.1091 H CH₃ CH₂OCH₂CH₂OCH₃ H HNSO₂N(CH₃)₂ 0 1.1092 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ H F NSO₂N(CH₃)₂ 0 1.1093 HCH₃ CH₂OCH₂CH₂OCH₂CH₃ H Cl NSO₂N(CH₃)₂ 0 1.1094 H CH₃ CH₂OCH₂CH₂OCH₂CH₃H H NSO₂N(CH₃)₂ 0 1.1095 H CH₃ CH₂CH₂OCH₃ H F NSO₂N(CH₃)₂ 0 1.1096 H CH₃CH₂CH₂OCH₃ H Cl NSO₂N(CH₃)₂ 0 1.1097 H CH₃ CH₂CH₂OCH₃ H H NSO₂N(CH₃)₂ 01.1098 H CH₃ CH₂OCH₂C≡CH H F NSO₂N(CH₃)₂ 0 1.1099 H CH₃ CH₂OCH₂C≡CH H ClNSO₂N(CH₃)₂ 0 1.1100 H CH₃ CH₂OCH₂C≡CH H H NSO₂N(CH₃)₂ 0 1.1101 H CH₃CH₂OCH₂C≡CCH₃ H F NSO₂N(CH₃)₂ 0 1.1102 H CH₃ CH₂OCH₂C≡CCH₃ H ClNSO₂N(CH₃)₂ 0 1.1103 H CH₃ CH₂OCH₂C≡CCH₃ H H NSO₂N(CH₃)₂ 0 1.1104 H CH₃CH₂CH₂CH₂OCH₃ H F NSO₂N(CH₃)₂ 0 1.1105 H CH₃ CH₂CH₂CH₂OCH₃ H ClNSO₂N(CH₃)₂ 0 1.1106 H CH₃ CH₂CH₂CH₂OCH₃ H H NSO₂N(CH₃)₂ 0 1.1107 H CH₃CH₂OCH₂OCH₃ H F NSO₂N(CH₃)₂ 0 1.1108 H CH₃ CH₂OCH₂OCH₃ H Cl NSO₂N(CH₃)₂0 1.1109 H CH₃ CH₂OCH₂OCH₃ H H NSO₂N(CH₃)₂ 0 1.1110 H CH₃CH₂N(CH₃)SO₂CH₃ H F NSO₂N(CH₃)₂ 0 1.1111 H CH₃ CH₂N(CH₃)SO₂CH₃ H ClNSO₂N(CH₃)₂ 0 1.1112 H CH₃ CH₂N(CH₃)SO₂CH₃ H H NSO₂N(CH₃)₂ 0 1.1113 HCH₃ CF₃ H F NSO₂N(CH₃)₂ 0 1.1114 H CH₃ CF₃ H Cl NSO₂N(CH₃)₂ 0 1.1115 HCH₃ CF₃ H H NSO₂N(CH₃)₂ 0 1.1116 H CH₃ CH₂OCH₂CF₃ H F NSO₂N(CH₃)₂ 01.1117 H CH₃ CH₂OCH₂CF₃ H Cl NSO₂N(CH₃)₂ 0 1.1118 H CH₃ CH₂OCH₂CF₃ H HNSO₂N(CH₃)₂ 0 1.1119 H CH₃ CH₂OCH₂Ph H F NSO₂N(CH₃)₂ 0 1.1120 H CH₃CH₂OCH₂Ph H Cl NSO₂N(CH₃)₂ 0 1.1121 H CH₃ CH₂OCH₂Ph H H NSO₂N(CH₃)₂ 01.1122 H CH₃ CH₂OCH₂CH═CH₂ H F NSO₂N(CH₃)₂ 0 1.1123 H CH₃ CH₂OCH₂CH═CH₂H Cl NSO₂N(CH₃)₂ 0 1.1124 H CH₃ CH₂OCH₂CH═CH₂ H H NSO₂N(CH₃)₂ 0 1.1125 HCH₃

H F NSO₂N(CH₃)₂ 0 1.1126 H CH₃

H Cl NSO₂N(CH₃)₂ 0 1.1127 H CH₃

H H NSO₂N(CH₃)₂ 0 1.1128 H CH₃

H F NSO₂N(CH₃)₂ 0 1.1129 H CH₃

H Cl NSO₂N(CH₃)₂ 0 1.1130 H CH₃

H H NSO₂N(CH₃)₂ 0 1.1131 H CH₃

H F NSO₂N(CH₃)₂ 0 1.1132 H CH₃

H Cl NSO₂N(CH₃)₂ 0 1.1133 H CH₃

H H NSO₂N(CH₃)₂ 0 1.1134 H CH₃

H F NSO₂N(CH₃)₂ 0 1.1135 H CH₃

H Cl NSO₂N(CH₃)₂ 0 1.1136 H CH₃

H H NSO₂N(CH₃)₂ 0 1.1137 H CH₃

H F NSO₂N(CH₃)₂ 0 1.1138 H CH₃

H Cl NSO₂N(CH₃)₂ 0 1.1139 H CH₃

H H NSO₂N(CH₃)₂ 0 1.1140 H CH₃

H F NSO₂N(CH₃)₂ 0 1.1141 H CH₃

H Cl NSO₂N(CH₃)₂ 0 1.1142 H CH₃

H H NSO₂N(CH₃)₂ 0 1.1143 H CH₃ CH₃ H F NSO₂N(CH₃)₂ 1 1.1144 H CH₃CH₂OCH₃ H F NSO₂N(CH₃)₂ 1 1.1145 H CH₃ CH₂OCH₂CH₂OCH₃ H F NSO₂N(CH₃)₂ 11.1146 H CH₃ CH₂CH₂CH₂OCH₃ H F NSO₂N(CH₃)₂ 1 1.1147 H CH₃ CH₂CH₃ H FNSO₂N(CH₃)₂ 1 1.1148 H CH₃ CH₃ H H NSO₂N(CH₃)₂ 1 1.1149 H CH₃ CH₂OCH₃ HH NSO₂N(CH₃)₂ 1 1.1150 H CH₃ CH₂OCH₂CH₂OCH₃ H H NSO₂N(CH₃)₂ 1 1.1151 HCH₃ CH₂CH₂CH₂OCH₃ H H NSO₂N(CH₃)₂ 1 1.1152 H CH₃ CH₂CH₃ H H NSO₂N(CH₃)₂1 1.1153 H H CH₃ H F

0 ¹H NMR (300 MHz; CDCl₃) δ 16.58 (s, 1H); 7.55 (m, 2H); 6.48 (m, 1H);6.40 (m, 1H); 2.94 (m, 1H): 2.72 (m, 1H); 2.50 (s, 3H); 0.90-0.65 (m,4H). 1.1154 H H CH₃ H F C(═C(CH₃)₂) 0 ¹H NMR (300 MHz; CDCl₃) δ 16.25(s, 1H); 7.56 (m, 2H); 6.52 (m, 1H); 6.45 (m, 1H); 4.20 (m, 1H); 3.98(m, 1H); 2.45 (s, 3H); 1.80 (s, 3H); 1.71 (s, 3H). 1.1155 H H CH₃ H HCH₂CH(COOCH₃) 0 R₇ = Br; ¹H NMR (300 MHz; CDCl₃) i.a. δ 7.44 (d, 2H);6.54 (t, 1H), 6.53 + 6.42 (2d, 1H); 3.71 + 3.68 (2s, 3H); 2.41 + 2.40(2s, 3H); tautomeric mixture. 1.1156 H H CH₃ H H CH₂CH(COOCH₃) 0 R₇ = H;NEt₃ salt (Example P14)

TABLE 2 Compounds of formula Ic: (Ic)

No. R₁ R₂ Z₁ R₃₀ X Y Physical data 2.0000 H H CH₂OCH₂CH₂OCH₃ H F CH₂2.0001 H H CH₂OCH₂CH₂OCH₃ H Cl CH₂ 2.0002 H H CH₂OCH₂CH₂OCH₃ H H CH₂2.0003 H H CH₂OCH₂CH₂OCH₂CH₃ H F CH₂ 2.0004 H H CH₂OCH₂CH₂OCH₂CH₃ H ClCH₂ 2.0005 H H CH₂OCH₂CH₂OCH₂CH₃ H H CH₂ 2.0006 H H CH₂N(CH₃)SO₂CH₃ H FCH₂ 2.0007 H H CH₂N(CH₃)SO₂CH₃ H Cl CH₂ 2.0008 H H CH₂N(CH₃)SO₂CH₃ H HCH₂ 2.0009 H H CH₂OCH₂Ph H F CH₂ 2.0010 H H CH₂OCH₂Ph H Cl CH₂ 2.0011 HH CH₂OCH₂Ph H H CH₂ 2.0012 H H CH₂OCH₂CH₂OH H F CH₂ 2.0013 H HCH₂OCH₂CH₂OH H Cl CH₂ 2.0014 H H CH₂OCH₂CH₂OH H H CH₂ 2.0015 H HCH₂OCH₂CH₂Cl H F CH₂ 2.0016 H H CH₂OCH₂CH₂Cl H Cl CH₂ 2.0017 H HCH₂OCH₂CH₂Cl H H CH₂ 2.0018 H H CH₂OCH₂CF₃ H F CH₂ 2.0019 H H CH₂OCH₂CF₃H Cl CH₂ 2.0020 H H CH₂OCH₂CF₃ H H CH₂ 2.0021 H H CH₂OCH₂CH═CH₂ H F CH₂2.0022 H H CH₂OCH₂CH═CH₂ H Cl CH₂ 2.0023 H H CH₂OCH₂CH═CH₂ H H CH₂2.0024 H H CH₂O(CO)CH₃ H F CH₂ 2.0025 H H CH₂O(CO)CH₃ H Cl CH₂ 2.0026 HH CH₂O(CO)CH₃ H H CH₂ 2.0027 H H CH₂OCH₂C≡CH H F CH₂ 2.0028 H HCH₂OCH₂C≡CH H Cl CH₂ 2.0029 H H CH₂OCH₂C≡CH H H CH₂ 2.0030 H HCH₂OCH₂C≡CCH₃ H F CH₂ 2.0031 H H CH₂OCH₂C≡CCH₃ H Cl CH₂ 2.0032 H HCH₂OCH₂C≡CCH₃ H H CH₂ 2.0033 H H

H F CH₂ 2.0034 H H

H Cl CH₂ 2.0035 H H

H H CH₂ 2.0036 H H

H F CH₂ 2.0037 H H

H Cl CH₂ 2.0038 H H

H H CH₂ 2.0039 H H

H F CH₂ 2.0040 H H

H Cl CH₂ 2.0041 H H

H H CH₂ 2.0042 H H

H F CH₂ 2.0043 H H

H Cl CH₂ 2.0044 H H

H H CH₂ 2.0045 H H

H F CH₂ 2.0046 H H

H Cl CH₂ 2.0047 H H

H H CH₂ 2.0048 H H

H F CH₂ 2.0049 H H

H Cl CH₂ 2.0050 H H

H H CH₂ 2.0051 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ H F CH₂ 2.0052 CH₃ CH₃CH₂OCH₂CH₂OCH₃ H Cl CH₂ 2.0053 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ H H CH₂ 2.0054 CH₃CH₃ CH₂OCH₂CH₂OCH₂CH₃ H F CH₂ 2.0055 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ H Cl CH₂2.0056 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ H H CH₂ 2.0057 CH₃ CH₃ CH₂N(CH₃)SO₂CH₃H F CH₂ 2.0058 CH₃ CH₃ CH₂N(CH₃)SO₂CH₃ H Cl CH₂ 2.0059 CH₃ CH₃CH₂N(CH₃)SO₂CH₃ H H CH₂ 2.0060 CH₃ CH₃ CH₂OCH₂Ph H F CH₂ 2.0061 CH₃ CH₃CH₂OCH₂Ph H Cl CH₂ 2.0062 CH₃ CH₃ CH₂OCH₂Ph H H CH₂ 2.0063 CH₃ CH₃CH₂OCH₂CH₂OH H F CH₂ 2.0064 CH₃ CH₃ CH₂OCH₂CH₂OH H Cl CH₂ 2.0065 CH₃ CH₃CH₂OCH₂CH₂OH H H CH₂ 2.0066 CH₃ CH₃ CH₂OCH₂CH₂Cl H F CH₂ 2.0067 CH₃ CH₃CH₂OCH₂CH₂Cl H Cl CH₂ 2.0068 CH₃ CH₃ CH₂OCH₂CH₂Cl H H CH₂ 2.0069 CH₃ CH₃CH₂OCH₂CF₃ H F CH₂ 2.0070 CH₃ CH₃ CH₂OCH₂CF₃ H Cl CH₂ 2.0071 CH₃ CH₃CH₂OCH₂CF₃ H H CH₂ 2.0072 CH₃ CH₃ CH₂OCH₂CH═CH₂ H F CH₂ 2.0073 CH₃ CH₃CH₂OCH₂CH═CH₂ H Cl CH₂ 2.0074 CH₃ CH₃ CH₂OCH₂CH═CH₂ H H CH₂ 2.0075 CH₃CH₃ CH₂O(CO)CH₃ H F CH₂ 2.0076 CH₃ CH₃ CH₂O(CO)CH₃ H Cl CH₂ 2.0077 CH₃CH₃ CH₂O(CO)CH₃ H H CH₂ 2.0078 CH₃ CH₃ CH₂OCH₂C≡CH H F CH₂ 2.0079 CH₃CH₃ CH₂OCH₂C≡CH H Cl CH₂ 2.0080 CH₃ CH₃ CH₂OCH₂C≡CH H H CH₂ 2.0081 CH₃CH₃ CH₂OCH₂C≡CCH₃ H F CH₂ 2.0082 CH₃ CH₃ CH₂OCH₂C≡CCH₃ H Cl CH₂ 2.0083CH₃ CH₃ CH₂OCH₂C≡CCH₃ H H CH₂ 2.0084 CH₃ CH₃

H F CH₂ 2.0085 CH₃ CH₃

H Cl CH₂ 2.0086 CH₃ CH₃

H H CH₂ 2.0087 CH₃ CH₃

H F CH₂ 2.0088 CH₃ CH₃

H Cl CH₂ 2.0089 CH₃ CH₃

H H CH₂ 2.0090 CH₃ CH₃

H F CH₂ 2.0091 CH₃ CH₃

H Cl CH₂ 2.0092 CH₃ CH₃

H H CH₂ 2.0093 CH₃ CH₃

H F CH₂ 2.0094 CH₃ CH₃

H Cl CH₂ 2.0095 CH₃ CH₃

H H CH₂ 2.0096 CH₃ CH₃

H F CH₂ 2.0097 CH₃ CH₃

H Cl CH₂ 2.0098 CH₃ CH₃

H H CH₂ 2.0099 CH₃ CH₃

H F CH₂ 2.0100 CH₃ CH₃

H Cl CH₂ 2.0101 CH₃ CH₃

H H CH₂ 2.0102 H CH₃ CH₂OCH₂CH₂OCH₃ H F CH₂ 2.0103 H CH₃ CH₂OCH₂CH₂OCH₃H Cl CH₂ 2.0104 H CH₃ CH₂OCH₂CH₂OCH₃ H H CH₂ 2.0105 H CH₃CH₂OCH₂CH₂OCH₂CH₃ H F CH₂ 2.0106 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ H Cl CH₂ 2.0107H CH₃ CH₂OCH₂CH₂OCH₂CH₃ H H CH₂ 2.0108 H CH₃ CH₂N(CH₃)SO₂CH₃ H F CH₂2.0109 H CH₃ CH₂N(CH₃)SO₂CH₃ H Cl CH₂ 2.0110 H CH₃ CH₂N(CH₃)SO₂CH₃ H HCH₂ 2.0111 H CH₃ CH₂OCH₂Ph H F CH₂ 2.0112 H CH₃ CH₂OCH₂Ph H Cl CH₂2.0113 H CH₃ CH₂OCH₂Ph H H CH₂ 2.0114 H CH₃ CH₂OCH₂CH₂OH H F CH₂ 2.0115H CH₃ CH₂OCH₂CH₂OH H Cl CH₂ 2.0116 H CH₃ CH₂OCH₂CH₂OH H H CH₂ 2.0117 HCH₃ CH₂OCH₂CH₂Cl H F CH₂ 2.0118 H CH₃ CH₂OCH₂CH₂Cl H Cl CH₂ 2.0119 H CH₃CH₂OCH₂CH₂Cl H H CH₂ 2.0120 H CH₃ CH₂OCH₂CF₃ H F CH₂ 2.0121 H CH₃CH₂OCH₂CF₃ H Cl CH₂ 2.0122 H CH₃ CH₂OCH₂CF₃ H H CH₂ 2.0123 H CH₃CH₂OCH₂CH═CH₂ H F CH₂ 2.0124 H CH₃ CH₂OCH₂CH═CH₂ H Cl CH₂ 2.0125 H CH₃CH₂OCH₂CH═CH₂ H H CH₂ 2.0126 H CH₃ CH₂O(CO)CH₃ H F CH₂ 2.0127 H CH₃CH₂O(CO)CH₃ H Cl CH₂ 2.0128 H CH₃ CH₂O(CO)CH₃ H H CH₂ 2.0129 H CH₃CH₂OCH₂C≡CH H F CH₂ 2.0130 H CH₃ CH₂OCH₂C≡CH H Cl CH₂ 2.0131 H CH₃CH₂OCH₂C≡CH H H CH₂ 2.0132 H CH₃ CH₂OCH₂C≡CCH₃ H F CH₂ 2.0133 H CH₃CH₂OCH₂C≡CCH₃ H Cl CH₂ 2.0134 H CH₃ CH₂OCH₂C≡CCH₃ H H CH₂ 2.0135 H CH₃

H F CH₂ 2.0136 H CH₃

H Cl CH₂ 2.0137 H CH₃

H H CH₂ 2.0138 H CH₃

H F CH₂ 2.0139 H CH₃

H Cl CH₂ 2.0140 H CH₃

H H CH₂ 2.0141 H CH₃

H F CH₂ 2.0142 H CH₃

H Cl CH₂ 2.0143 H CH₃

H H CH₂ 2.0144 H CH₃

H F CH₂ 2.0145 H CH₃

H Cl CH₂ 2.0146 H CH₃

H H CH₂ 2.0147 H CH₃

H F CH₂ 2.0148 H CH₃

H Cl CH₂ 2.0149 H CH₃

H H CH₂ 2.0150 H CH₃

H F CH₂ 2.0151 H CH₃

H Cl CH₂ 2.0152 H CH₃

H H CH₂ 2.0153 H H CH₂OCH₂CH₂OCH₃ CH₃ F CH₂ 2.0154 H H CH₂OCH₂CH₂OCH₃CH₃ Cl CH₂ 2.0155 H H CH₂OCH₂CH₂OCH₃ CH₃ H CH₂ 2.0156 H HCH₂OCH₂CH₂OCH₂CH₃ CH₃ F CH₂ 2.0157 H H CH₂OCH₂CH₂OCH₂CH₃ CH₃ Cl CH₂2.0158 H H CH₂OCH₂CH₂OCH₂CH₃ CH₃ H CH₂ 2.0159 H H CH₂N(CH₃)SO₂CH₃ CH₃ FCH₂ 2.0160 H H CH₂N(CH₃)SO₂CH₃ CH₃ Cl CH₂ 2.0161 H H CH₂N(CH₃)SO₂CH₃ CH₃H CH₂ 2.0162 H H CH₂OCH₂Ph CH₃ F CH₂ 2.0163 H H CH₂OCH₂Ph CH₃ Cl CH₂2.0164 H H CH₂OCH₂Ph CH₃ H CH₂ 2.0165 H H CH₂OCH₂CH₂OH CH₃ F CH₂ 2.0166H H CH₂OCH₂CH₂OH CH₃ Cl CH₂ 2.0167 H H CH₂OCH₂CH₂OH CH₃ H CH₂ 2.0168 H HCH₂OCH₂CH₂Cl CH₃ F CH₂ 2.0169 H H CH₂OCH₂CH₂Cl CH₃ Cl CH₂ 2.0170 H HCH₂OCH₂CH₂Cl CH₃ H CH₂ 2.0171 H H CH₂OCH₂CF₃ CH₃ F CH₂ 2.0172 H HCH₂OCH₂CF₃ CH₃ Cl CH₂ 2.0173 H H CH₂OCH₂CF₃ CH₃ H CH₂ 2.0174 H HCH₂OCH₂CH═CH₂ CH₃ F CH₂ 2.0175 H H CH₂OCH₂CH═CH₂ CH₃ Cl CH₂ 2.0176 H HCH₂OCH₂CH═CH₂ CH₃ H CH₂ 2.0177 H H CH₂O(CO)CH₃ CH₃ F CH₂ 2.0178 H HCH₂O(CO)CH₃ CH₃ Cl CH₂ 2.0179 H H CH₂O(CO)CH₃ CH₃ H CH₂ 2.0180 H HCH₂OCH₂C≡CH CH₃ F CH₂ 2.0181 H H CH₂OCH₂C≡CH CH₃ Cl CH₂ 2.0182 H HCH₂OCH₂C≡CH CH₃ H CH₂ 2.0183 H H CH₂OCH₂C≡CCH₃ CH₃ F CH₂ 2.0184 H HCH₂OCH₂C≡CCH₃ CH₃ Cl CH₂ 2.0185 H H CH₂OCH₂C≡CCH₃ CH₃ H CH₂ 2.0186 H H

CH₃ F CH₂ 2.0187 H H

CH₃ Cl CH₂ 2.0188 H H

CH₃ H CH₂ 2.0189 H H

CH₃ F CH₂ 2.0190 H H

CH₃ Cl CH₂ 2.0191 H H

CH₃ H CH₂ 2.0192 H H

CH₃ F CH₂ 2.0193 H H

CH₃ Cl CH₂ 2.0194 H H

CH₃ H CH₂ 2.0195 H H

CH₃ F CH₂ 2.0196 H H

CH₃ Cl CH₂ 2.0197 H H

CH₃ H CH₂ 2.0198 H H

CH₃ F CH₂ 2.0199 H H

CH₃ Cl CH₂ 2.0200 H H

CH₃ H CH₂ 2.0201 H H

CH₃ F CH₂ 2.0202 H H

CH₃ Cl CH₂ 2.0203 H H

CH₃ H CH₂ 2.0204 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ CH₃ F CH₂ 2.0205 CH₃ CH₃CH₂OCH₂CH₂OCH₃ CH₃ Cl CH₂ 2.0206 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ CH₃ H CH₂ 2.0207CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ CH₃ F CH₂ 2.0208 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ CH₃Cl CH₂ 2.0209 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ CH₃ H CH₂ 2.0210 CH₃ CH₃CH₂N(CH₃)SO₂CH₃ CH₃ F CH₂ 2.0211 CH₃ CH₃ CH₂N(CH₃)SO₂CH₃ CH₃ Cl CH₂2.0212 CH₃ CH₃ CH₂N(CH₃)SO₂CH₃ CH₃ H CH₂ 2.0213 CH₃ CH₃ CH₂OCH₂Ph CH₃ FCH₂ 2.0214 CH₃ CH₃ CH₂OCH₂Ph CH₃ Cl CH₂ 2.0215 CH₃ CH₃ CH₂OCH₂Ph CH₃ HCH₂ 2.0216 CH₃ CH₃ CH₂OCH₂CH₂OH CH₃ F CH₂ 2.0217 CH₃ CH₃ CH₂OCH₂CH₂OHCH₃ Cl CH₂ 2.0218 CH₃ CH₃ CH₂OCH₂CH₂OH CH₃ H CH₂ 2.0219 CH₃ CH₃CH₂OCH₂CH₂Cl CH₃ F CH₂ 2.0220 CH₃ CH₃ CH₂OCH₂CH₂Cl CH₃ Cl CH₂ 2.0221 CH₃CH₃ CH₂OCH₂CH₂Cl CH₃ H CH₂ 2.0222 CH₃ CH₃ CH₂OCH₂CF₃ CH₃ F CH₂ 2.0223CH₃ CH₃ CH₂OCH₂CF₃ CH₃ Cl CH₂ 2.0224 CH₃ CH₃ CH₂OCH₂CF₃ CH₃ H CH₂ 2.0225CH₃ CH₃ CH₂OCH₂CH═CH₂ CH₃ F CH₂ 2.0226 CH₃ CH₃ CH₂OCH₂CH═CH₂ CH₃ Cl CH₂2.0227 CH₃ CH₃ CH₂OCH₂CH═CH₂ CH₃ H CH₂ 2.0228 CH₃ CH₃ CH₂O(CO)CH₃ CH₃ FCH₂ 2.0229 CH₃ CH₃ CH₂O(CO)CH₃ CH₃ Cl CH₂ 2.0230 CH₃ CH₃ CH₂O(CO)CH₃ CH₃H CH₂ 2.0231 CH₃ CH₃ CH₂OCH₂C≡CH CH₃ F CH₂ 2.0232 CH₃ CH₃ CH₂OCH₂C≡CHCH₃ Cl CH₂ 2.0233 CH₃ CH₃ CH₂OCH₂C≡CH CH₃ H CH₂ 2.0234 CH₃ CH₃CH₂OCH₂C≡CCH₃ CH₃ F CH₂ 2.0235 CH₃ CH₃ CH₂OCH₂C≡CCH₃ CH₃ Cl CH₂ 2.0236CH₃ CH₃ CH₂OCH₂C≡CCH₃ CH₃ H CH₂ 2.0237 CH₃ CH₃

CH₃ F CH₂ 2.0238 CH₃ CH₃

CH₃ Cl CH₂ 2.0239 CH₃ CH₃

CH₃ H CH₂ 2.0240 CH₃ CH₃

CH₃ F CH₂ 2.0241 CH₃ CH₃

CH₃ Cl CH₂ 2.0242 CH₃ CH₃

CH₃ H CH₂ 2.0243 CH₃ CH₃

CH₃ F CH₂ 2.0244 CH₃ CH₃

CH₃ Cl CH₂ 2.0245 CH₃ CH₃

CH₃ H CH₂ 2.0246 CH₃ CH₃

CH₃ F CH₂ 2.0247 CH₃ CH₃

CH₃ Cl CH₂ 2.0248 CH₃ CH₃

CH₃ H CH₂ 2.0249 CH₃ CH₃

CH₃ F CH₂ 2.0250 CH₃ CH₃

CH₃ Cl CH₂ 2.0251 CH₃ CH₃

CH₃ H CH₂ 2.0252 CH₃ CH₃

CH₃ F CH₂ 2.0253 CH₃ CH₃

CH₃ Cl CH₂ 2.0254 CH₃ CH₃

CH₃ H CH₂ 2.0255 H CH₃ CH₂OCH₂CH₂OCH₃ CH₃ F CH₂ 2.0256 H CH₃CH₂OCH₂CH₂OCH₃ CH₃ Cl CH₂ 2.0257 H CH₃ CH₂OCH₂CH₂OCH₃ CH₃ H CH₂ 2.0258 HCH₃ CH₂OCH₂CH₂OCH₂CH₃ CH₃ F CH₂ 2.0259 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ CH₃ ClCH₂ 2.0260 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ CH₃ H CH₂ 2.0261 H CH₃CH₂N(CH₃)SO₂CH₃ CH₃ F CH₂ 2.0262 H CH₃ CH₂N(CH₃)SO₂CH₃ CH₃ Cl CH₂ 2.0263H CH₃ CH₂N(CH₃)SO₂CH₃ CH₃ H CH₂ 2.0264 H CH₃ CH₂OCH₂Ph CH₃ F CH₂ 2.0265H CH₃ CH₂OCH₂Ph CH₃ Cl CH₂ 2.0266 H CH₃ CH₂OCH₂Ph CH₃ H CH₂ 2.0267 H CH₃CH₂OCH₂CH₂OH CH₃ F CH₂ 2.0268 H CH₃ CH₂OCH₂CH₂OH CH₃ Cl CH₂ 2.0269 H CH₃CH₂OCH₂CH₂OH CH₃ H CH₂ 2.0270 H CH₃ CH₂OCH₂CH₂Cl CH₃ F CH₂ 2.0271 H CH₃CH₂OCH₂CH₂Cl CH₃ Cl CH₂ 2.0272 H CH₃ CH₂OCH₂CH₂Cl CH₃ H CH₂ 2.0273 H CH₃CH₂OCH₂CF₃ CH₃ F CH₂ 2.0274 H CH₃ CH₂OCH₂CF₃ CH₃ Cl CH₂ 2.0275 H CH₃CH₂OCH₂CF₃ CH₃ H CH₂ 2.0276 H CH₃ CH₂OCH₂CH═CH₂ CH₃ F CH₂ 2.0277 H CH₃CH₂OCH₂CH═CH₂ CH₃ Cl CH₂ 2.0278 H CH₃ CH₂OCH₂CH═CH₂ CH₃ H CH₂ 2.0279 HCH₃ CH₂O(CO)CH₃ CH₃ F CH₂ 2.0280 H CH₃ CH₂O(CO)CH₃ CH₃ Cl CH₂ 2.0281 HCH₃ CH₂O(CO)CH₃ CH₃ H CH₂ 2.0282 H CH₃ CH₂OCH₂C≡CH CH₃ F CH₂ 2.0283 HCH₃ CH₂OCH₂C≡CH CH₃ Cl CH₂ 2.0284 H CH₃ CH₂OCH₂C≡CH CH₃ H CH₂ 2.0285 HCH₃ CH₂OCH₂C≡CCH₃ CH₃ F CH₂ 2.0286 H CH₃ CH₂OCH₂C≡CCH₃ CH₃ Cl CH₂ 2.0287H CH₃ CH₂OCH₂C≡CCH₃ CH₃ H CH₂ 2.0288 H CH₃

CH₃ F CH₂ 2.0289 H CH₃

CH₃ Cl CH₂ 2.0290 H CH₃

CH₃ H CH₂ 2.0291 H CH₃

CH₃ F CH₂ 2.0292 H CH₃

CH₃ Cl CH₂ 2.0293 H CH₃

CH₃ H CH₂ 2.0294 H CH₃

CH₃ F CH₂ 2.0295 H CH₃

CH₃ Cl CH₂ 2.0296 H CH₃

CH₃ H CH₂ 2.0297 H CH₃

CH₃ F CH₂ 2.0298 H CH₃

CH₃ Cl CH₂ 2.0299 H CH₃

CH₃ H CH₂ 2.0300 H CH₃

CH₃ F CH₂ 2.0301 H CH₃

CH₃ Cl CH₂ 2.0302 H CH₃

CH₃ H CH₂ 2.0303 H CH₃

CH₃ F CH₂ 2.0304 H CH₃

CH₃ Cl CH₂ 2.0305 H CH₃

CH₃ H CH₂

TABLE 3 Compounds of formula Id: (Id)

No. R₁ R₂ Z₁ R₃₀ X Y p Phys. data, remarks 3.0000 H H CH₂OCH₂CH₂OCH₃ H FCH₂ 0 3.0001 H H CH₂OCH₂CH₂OCH₃ H Cl CH₂ 0 3.0002 H H CH₂OCH₂CH₂OCH₃ H HCH₂ 0 3.0003 H H CH₂OCH₂CH₂OCH₂CH₃ H F CH₂ 0 3.0004 H HCH₂OCH₂CH₂OCH₂CH₃ H Cl CH₂ 0 3.0005 H H CH₂OCH₂CH₂OCH₂CH₃ H H CH₂ 03.0006 H H CH₂N(CH₃)SO₂CH₃ H F CH₂ 0 3.0007 H H CH₂N(CH₃)SO₂CH₃ H Cl CH₂0 3.0008 H H CH₂N(CH₃)SO₂CH₃ H H CH₂ 0 3.0009 H H CH₂OCH₂Ph H F CH₂ 03.0010 H H CH₂OCH₂Ph H Cl CH₂ 0 3.0011 H H CH₂OCH₂Ph H H CH₂ 0 3.0012 HH CH₂OCH₂CH₂OH H F CH₂ 0 3.0013 H H CH₂OCH₂CH₂OH H Cl CH₂ 0 3.0014 H HCH₂OCH₂CH₂OH H H CH₂ 0 3.0015 H H CH₂OCH₂CH₂Cl H F CH₂ 0 3.0016 H HCH₂OCH₂CH₂Cl H Cl CH₂ 0 3.0017 H H CH₂OCH₂CH₂Cl H H CH₂ 0 3.0018 H HCH₂OCH₂CF₃ H F CH₂ 0 3.0019 H H CH₂OCH₂CF₃ H Cl CH₂ 0 3.0020 H HCH₂OCH₂CF₃ H H CH₂ 0 3.0021 H H CH₂OCH₂CH═CH₂ H F CH₂ 0 3.0022 H HCH₂OCH₂CH═CH₂ H Cl CH₂ 0 3.0023 H H CH₂OCH₂CH═CH₂ H H CH₂ 0 3.0024 H HCH₂O(CO)CH₃ H F CH₂ 0 3.0025 H H CH₂O(CO)CH₃ H Cl CH₂ 0 3.0026 H HCH₂O(CO)CH₃ H H CH₂ 0 3.0027 H H CH₂OCH₂C≡CH H F CH₂ 0 3.0028 H HCH₂OCH₂C≡CH H Cl CH₂ 0 3.0029 H H CH₂OCH₂C≡CH H H CH₂ 0 3.0030 H HCH₂OCH₂C≡CCH₃ H F CH₂ 0 3.0031 H H CH₂OCH₂C≡CCH₃ H Cl CH₂ 0 3.0032 H HCH₂OCH₂C≡CCH₃ H H CH₂ 0 3.0033 H H

H F CH₂ 0 3.0034 H H

H Cl CH₂ 0 3.0035 H H

H H CH₂ 0 3.0036 H H

H F CH₂ 0 3.0037 H H

H Cl CH₂ 0 3.0038 H H

H H CH₂ 0 3.0039 H H

H F CH₂ 0 3.0040 H H

H Cl CH₂ 0 3.0041 H H

H H CH₂ 0 3.0042 H H

H F CH₂ 0 3.0043 H H

H Cl CH₂ 0 3.0044 H H

H H CH₂ 0 3.0045 H H

H F CH₂ 0 3.0046 H H

H Cl CH₂ 0 3.0047 H H

H H CH₂ 0 3.0048 H H

H F CH₂ 0 3.0049 H H

H Cl CH₂ 0 3.0050 H H

H H CH₂ 0 3.0051 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ H F CH₂ 0 3.0052 CH₃ CH₃CH₂OCH₂CH₂OCH₃ H Cl CH₂ 0 3.0053 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ H H CH₂ 0 3.0054CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ H F CH₂ 0 3.0055 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ HCl CH₂ 0 3.0056 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ H H CH₂ 0 3.0057 CH₃ CH₃CH₂N(CH₃)SO₂CH₃ H F CH₂ 0 3.0058 CH₃ CH₃ CH₂N(CH₃)SO₂CH₃ H Cl CH₂ 03.0059 CH₃ CH₃ CH₂N(CH₃)SO₂CH₃ H H CH₂ 0 3.0060 CH₃ CH₃ CH₂OCH₂Ph H FCH₂ 0 3.0061 CH₃ CH₃ CH₂OCH₂Ph H Cl CH₂ 0 3.0062 CH₃ CH₃ CH₂OCH₂Ph H HCH₂ 0 3.0063 CH₃ CH₃ CH₂OCH₂CH₂OH H F CH₂ 0 3.0064 CH₃ CH₃ CH₂OCH₂CH₂OHH Cl CH₂ 0 3.0065 CH₃ CH₃ CH₂OCH₂CH₂OH H H CH₂ 0 3.0066 CH₃ CH₃CH₂OCH₂CH₂Cl H F CH₂ 0 3.0067 CH₃ CH₃ CH₂OCH₂CH₂Cl H Cl CH₂ 0 3.0068 CH₃CH₃ CH₂OCH₂CH₂Cl H H CH₂ 0 3.0069 CH₃ CH₃ CH₂OCH₂CF₃ H F CH₂ 0 3.0070CH₃ CH₃ CH₂OCH₂CF₃ H Cl CH₂ 0 3.0071 CH₃ CH₃ CH₂OCH₂CF₃ H H CH₂ 0 3.0072CH₃ CH₃ CH₂OCH₂CH═CH₂ H F CH₂ 0 3.0073 CH₃ CH₃ CH₂OCH₂CH═CH₂ H Cl CH₂ 03.0074 CH₃ CH₃ CH₂OCH₂CH═CH₂ H H CH₂ 0 3.0075 CH₃ CH₃ CH₂O(CO)CH₃ H FCH₂ 0 3.0076 CH₃ CH₃ CH₂O(CO)CH₃ H Cl CH₂ 0 3.0077 CH₃ CH₃ CH₂O(CO)CH₃ HH CH₂ 0 3.0078 CH₃ CH₃ CH₂OCH₂C≡CH H F CH₂ 0 3.0079 CH₃ CH₃ CH₂OCH₂C≡CHH Cl CH₂ 0 3.0080 CH₃ CH₃ CH₂OCH₂C≡CH H H CH₂ 0 3.0081 CH₃ CH₃CH₂OCH₂C≡CCH₃ H F CH₂ 0 3.0082 CH₃ CH₃ CH₂OCH₂C≡CCH₃ H Cl CH₂ 0 3.0083CH₃ CH₃ CH₂OCH₂C≡CCH₃ H H CH₂ 0 3.0084 CH₃ CH₃

H F CH₂ 0 3.0085 CH₃ CH₃

H Cl CH₂ 0 3.0086 CH₃ CH₃

H H CH₂ 0 3.0087 CH₃ CH₃

H F CH₂ 0 3.0088 CH₃ CH₃

H Cl CH₂ 0 3.0089 CH₃ CH₃

H H CH₂ 0 3.0090 CH₃ CH₃

H F CH₂ 0 3.0091 CH₃ CH₃

H Cl CH₂ 0 3.0092 CH₃ CH₃

H H CH₂ 0 3.0093 CH₃ CH₃

H F CH₂ 0 3.0094 CH₃ CH₃

H Cl CH₂ 0 3.0095 CH₃ CH₃

H H CH₂ 0 3.0096 CH₃ CH₃

H F CH₂ 0 3.0097 CH₃ CH₃

H Cl CH₂ 0 3.0098 CH₃ CH₃

H H CH₂ 0 3.0099 CH₃ CH₃

H F CH₂ 0 3.0100 CH₃ CH₃

H Cl CH₂ 0 3.0101 CH₃ CH₃

H H CH₂ 0 3.0102 H CH₃ CH₂OCH₂CH₂OCH₃ H F CH₂ 0 3.0103 H CH₃CH₂OCH₂CH₂OCH₃ H Cl CH₂ 0 3.0104 H CH₃ CH₂OCH₂CH₂OCH₃ H H CH₂ 0 3.0105 HCH₃ CH₂OCH₂CH₂OCH₂CH₃ H F CH₂ 0 3.0106 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ H Cl CH₂0 3.0107 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ H H CH₂ 0 3.0108 H CH₃ CH₂N(CH₃)SO₂CH₃H F CH₂ 0 3.0109 H CH₃ CH₂N(CH₃)SO₂CH₃ H Cl CH₂ 0 3.0110 H CH₃CH₂N(CH₃)SO₂CH₃ H H CH₂ 0 3.0111 H CH₃ CH₂OCH₂Ph H F CH₂ 0 3.0112 H CH₃CH₂OCH₂Ph H Cl CH₂ 0 3.0113 H CH₃ CH₂OCH₂Ph H H CH₂ 0 3.0114 H CH₃CH₂OCH₂CH₂OH H F CH₂ 0 3.0115 H CH₃ CH₂OCH₂CH₂OH H Cl CH₂ 0 3.0116 H CH₃CH₂OCH₂CH₂OH H H CH₂ 0 3.0117 H CH₃ CH₂OCH₂CH₂Cl H F CH₂ 0 3.0118 H CH₃CH₂OCH₂CH₂Cl H Cl CH₂ 0 3.0119 H CH₃ CH₂OCH₂CH₂Cl H H CH₂ 0 3.0120 H CH₃CH₂OCH₂CF₃ H F CH₂ 0 3.0121 H CH₃ CH₂OCH₂CF₃ H Cl CH₂ 0 3.0122 H CH₃CH₂OCH₂CF₃ H H CH₂ 0 3.0123 H CH₃ CH₂OCH₂CH═CH₂ H F CH₂ 0 3.0124 H CH₃CH₂OCH₂CH═CH₂ H Cl CH₂ 0 3.0125 H CH₃ CH₂OCH₂CH═CH₂ H H CH₂ 0 3.0126 HCH₃ CH₂O(CO)CH₃ H F CH₂ 0 3.0127 H CH₃ CH₂O(CO)CH₃ H Cl CH₂ 0 3.0128 HCH₃ CH₂O(CO)CH₃ H H CH₂ 0 3.0129 H CH₃ CH₂OCH₂C≡CH H F CH₂ 0 3.0130 HCH₃ CH₂OCH₂C≡CH H Cl CH₂ 0 3.0131 H CH₃ CH₂OCH₂C≡CH H H CH₂ 0 3.0132 HCH₃ CH₂OCH₂C≡CCH₃ H F CH₂ 0 3.0133 H CH₃ CH₂OCH₂C≡CCH₃ H Cl CH₂ 0 3.0134H CH₃ CH₂OCH₂C≡CCH₃ H H CH₂ 0 3.0135 H CH₃

H F CH₂ 0 3.0136 H CH₃

H Cl CH₂ 0 3.0137 H CH₃

H H CH₂ 0 3.0138 H CH₃

H F CH₂ 0 3.0139 H CH₃

H Cl CH₂ 0 3.0140 H CH₃

H H CH₂ 0 3.0141 H CH₃

H F CH₂ 0 3.0142 H CH₃

H Cl CH₂ 0 3.0143 H CH₃

H H CH₂ 0 3.0144 H CH₃

H F CH₂ 0 3.0145 H CH₃

H Cl CH₂ 0 3.0146 H CH₃

H H CH₂ 0 3.0147 H CH₃

H F CH₂ 0 3.0148 H CH₃

H Cl CH₂ 0 3.0149 H CH₃

H H CH₂ 0 3.0150 H CH₃

H F CH₂ 0 3.0151 H CH₃

H Cl CH₂ 0 3.0152 H CH₃

H H CH₂ 0 3.0153 H H CH₂OCH₂CH₂OCH₃ CH₃ F CH₂ 0 3.0154 H HCH₂OCH₂CH₂OCH₃ CH₃ Cl CH₂ 0 3.0155 H H CH₂OCH₂CH₂OCH₃ CH₃ H CH₂ 0 3.0156H H CH₂OCH₂CH₂OCH₂CH₃ CH₃ F CH₂ 0 3.0157 H H CH₂OCH₂CH₂OCH₂CH₃ CH₃ ClCH₂ 0 3.0158 H H CH₂OCH₂CH₂OCH₂CH₃ CH₃ H CH₂ 0 3.0159 H HCH₂N(CH₃)SO₂CH₃ CH₃ F CH₂ 0 3.0160 H H CH₂N(CH₃)SO₂CH₃ CH₃ Cl CH₂ 03.0161 H H CH₂N(CH₃)SO₂CH₃ CH₃ H CH₂ 0 3.0162 H H CH₂OCH₂Ph CH₃ F CH₂ 03.0163 H H CH₂OCH₂Ph CH₃ Cl CH₂ 0 3.0164 H H CH₂OCH₂Ph CH₃ H CH₂ 03.0165 H H CH₂OCH₂CH₂OH CH₃ F CH₂ 0 3.0166 H H CH₂OCH₂CH₂OH CH₃ Cl CH₂ 03.0167 H H CH₂OCH₂CH₂OH CH₃ H CH₂ 0 3.0168 H H CH₂OCH₂CH₂Cl CH₃ F CH₂ 03.0169 H H CH₂OCH₂CH₂Cl CH₃ Cl CH₂ 0 3.0170 H H CH₂OCH₂CH₂Cl CH₃ H CH₂ 03.0171 H H CH₂OCH₂CF₃ CH₃ F CH₂ 0 3.0172 H H CH₂OCH₂CF₃ CH₃ Cl CH₂ 03.0173 H H CH₂OCH₂CF₃ CH₃ H CH₂ 0 3.0174 H H CH₂OCH₂CH═CH₂ CH₃ F CH₂ 03.0175 H H CH₂OCH₂CH═CH₂ CH₃ Cl CH₂ 0 3.0176 H H CH₂OCH₂CH═CH₂ CH₃ H CH₂0 3.0177 H H CH₂O(CO)CH₃ CH₃ F CH₂ 0 3.0178 H H CH₂O(CO)CH₃ CH₃ Cl CH₂ 03.0179 H H CH₂O(CO)CH₃ CH₃ H CH₂ 0 3.0180 H H CH₂OCH₂C≡CH CH₃ F CH₂ 03.0181 H H CH₂OCH₂C≡CH CH₃ Cl CH₂ 0 3.0182 H H CH₂OCH₂C≡CH CH₃ H CH₂ 03.0183 H H CH₂OCH₂C≡CCH₃ CH₃ F CH₂ 0 3.0184 H H CH₂OCH₂C≡CCH₃ CH₃ Cl CH₂0 3.0185 H H CH₂OCH₂C≡CCH₃ CH₃ H CH₂ 0 3.0186 H H

CH₃ F CH₂ 0 3.0187 H H

CH₃ Cl CH₂ 0 3.0188 H H

CH₃ H CH₂ 0 3.0189 H H

CH₃ F CH₂ 0 3.0190 H H

CH₃ Cl CH₂ 0 3.0191 H H

CH₃ H CH₂ 0 3.0192 H H

CH₃ F CH₂ 0 3.0193 H H

CH₃ Cl CH₂ 0 3.0194 H H

CH₃ H CH₂ 0 3.0195 H H

CH₃ F CH₂ 0 3.0196 H H

CH₃ Cl CH₂ 0 3.0197 H H

CH₃ H CH₂ 0 3.0198 H H

CH₃ F CH₂ 0 3.0199 H H

CH₃ Cl CH₂ 0 3.0200 H H

CH₃ H CH₂ 0 3.0201 H H

CH₃ F CH₂ 0 3.0202 H H

CH₃ Cl CH₂ 0 3.0203 H H

CH₃ H CH₂ 0 3.0204 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ CH₃ F CH₂ 0 3.0205 CH₃ CH₃CH₂OCH₂CH₂OCH₃ CH₃ Cl CH₂ 0 3.0206 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ CH₃ H CH₂ 03.0207 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ CH₃ F CH₂ 0 3.0208 CH₃ CH₃CH₂OCH₂CH₂OCH₂CH₃ CH₃ Cl CH₂ 0 3.0209 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ CH₃ HCH₂ 0 3.0210 CH₃ CH₃ CH₂N(CH₃)SO₂CH₃ CH₃ F CH₂ 0 3.0211 CH₃ CH₃CH₂N(CH₃)SO₂CH₃ CH₃ Cl CH₂ 0 3.0212 CH₃ CH₃ CH₂N(CH₃)SO₂CH₃ CH₃ H CH₂ 03.0213 CH₃ CH₃ CH₂OCH₂Ph CH₃ F CH₂ 0 3.0214 CH₃ CH₃ CH₂OCH₂Ph CH₃ Cl CH₂0 3.0215 CH₃ CH₃ CH₂OCH₂Ph CH₃ H CH₂ 0 3.0216 CH₃ CH₃ CH₂OCH₂CH₂OH CH₃ FCH₂ 0 3.0217 CH₃ CH₃ CH₂OCH₂CH₂OH CH₃ Cl CH₂ 0 3.0218 CH₃ CH₃CH₂OCH₂CH₂OH CH₃ H CH₂ 0 3.0219 CH₃ CH₃ CH₂OCH₂CH₂Cl CH₃ F CH₂ 0 3.0220CH₃ CH₃ CH₂OCH₂CH₂Cl CH₃ Cl CH₂ 0 3.0221 CH₃ CH₃ CH₂OCH₂CH₂Cl CH₃ H CH₂0 3.0222 CH₃ CH₃ CH₂OCH₂CF₃ CH₃ F CH₂ 0 3.0223 CH₃ CH₃ CH₂OCH₂CF₃ CH₃ ClCH₂ 0 3.0224 CH₃ CH₃ CH₂OCH₂CF₃ CH₃ H CH₂ 0 3.0225 CH₃ CH₃ CH₂OCH₂CH═CH₂CH₃ F CH₂ 0 3.0226 CH₃ CH₃ CH₂OCH₂CH═CH₂ CH₃ Cl CH₂ 0 3.0227 CH₃ CH₃CH₂OCH₂CH═CH₂ CH₃ H CH₂ 0 3.0228 CH₃ CH₃ CH₂O(CO)CH₃ CH₃ F CH₂ 0 3.0229CH₃ CH₃ CH₂O(CO)CH₃ CH₃ Cl CH₂ 0 3.0230 CH₃ CH₃ CH₂O(CO)CH₃ CH₃ H CH₂ 03.0231 CH₃ CH₃ CH₂OCH₂C≡CH CH₃ F CH₂ 0 3.0232 CH₃ CH₃ CH₂OCH₂C≡CH CH₃ ClCH₂ 0 3.0233 CH₃ CH₃ CH₂OCH₂C≡CH CH₃ H CH₂ 0 3.0234 CH₃ CH₃CH₂OCH₂C≡CCH₃ CH₃ F CH₂ 0 3.0235 CH₃ CH₃ CH₂OCH₂C≡CCH₃ CH₃ Cl CH₂ 03.0236 CH₃ CH₃ CH₂OCH₂C≡CCH₃ CH₃ H CH₂ 0 3.0237 CH₃ CH₃

CH₃ F CH₂ 0 3.0238 CH₃ CH₃

CH₃ Cl CH₂ 0 3.0239 CH₃ CH₃

CH₃ H CH₂ 0 3.0240 CH₃ CH₃

CH₃ F CH₂ 0 3.0241 CH₃ CH₃

CH₃ Cl CH₂ 0 3.0242 CH₃ CH₃

CH₃ H CH₂ 0 3.0243 CH₃ CH₃

CH₃ F CH₂ 0 3.0244 CH₃ CH₃

CH₃ Cl CH₂ 0 3.0245 CH₃ CH₃

CH₃ H CH₂ 0 3.0246 CH₃ CH₃

CH₃ F CH₂ 0 3.0247 CH₃ CH₃

CH₃ Cl CH₂ 0 3.0248 CH₃ CH₃

CH₃ H CH₂ 0 3.0249 CH₃ CH₃

CH₃ F CH₂ 0 3.0250 CH₃ CH₃

CH₃ Cl CH₂ 0 3.0251 CH₃ CH₃

CH₃ H CH₂ 0 3.0252 CH₃ CH₃

CH₃ F CH₂ 0 3.0253 CH₃ CH₃

CH₃ Cl CH₂ 0 3.0254 CH₃ CH₃

CH₃ H CH₂ 0 3.0255 H CH₃ CH₂OCH₂CH₂OCH₃ CH₃ F CH₂ 0 3.0256 H CH₃CH₂OCH₂CH₂OCH₃ CH₃ Cl CH₂ 0 3.0257 H CH₃ CH₂OCH₂CH₂OCH₃ CH₃ H CH₂ 03.0258 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ CH₃ F CH₂ 0 3.0259 H CH₃CH₂OCH₂CH₂OCH₂CH₃ CH₃ Cl CH₂ 0 3.0260 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ CH₃ H CH₂0 3.0261 H CH₃ CH₂N(CH₃)SO₂CH₃ CH₃ F CH₂ 0 3.0262 H CH₃ CH₂N(CH₃)SO₂CH₃CH₃ Cl CH₂ 0 3.0263 H CH₃ CH₂N(CH₃)SO₂CH₃ CH₃ H CH₂ 0 3.0264 H CH₃CH₂OCH₂Ph CH₃ F CH₂ 0 3.0265 H CH₃ CH₂OCH₂Ph CH₃ Cl CH₂ 0 3.0266 H CH₃CH₂OCH₂Ph CH₃ H CH₂ 0 3.0267 H CH₃ CH₂OCH₂CH₂OH CH₃ F CH₂ 0 3.0268 H CH₃CH₂OCH₂CH₂OH CH₃ Cl CH₂ 0 3.0269 H CH₃ CH₂OCH₂CH₂OH CH₃ H CH₂ 0 3.0270 HCH₃ CH₂OCH₂CH₂Cl CH₃ F CH₂ 0 3.0271 H CH₃ CH₂OCH₂CH₂Cl CH₃ Cl CH₂ 03.0272 H CH₃ CH₂OCH₂CH₂Cl CH₃ H CH₂ 0 3.0273 H CH₃ CH₂OCH₂CF₃ CH₃ F CH₂0 3.0274 H CH₃ CH₂OCH₂CF₃ CH₃ Cl CH₂ 0 3.0275 H CH₃ CH₂OCH₂CF₃ CH₃ H CH₂0 3.0276 H CH₃ CH₂OCH₂CH═CH₂ CH₃ F CH₂ 0 3.0277 H CH₃ CH₂OCH₂CH═CH₂ CH₃Cl CH₂ 0 3.0278 H CH₃ CH₂OCH₂CH═CH₂ CH₃ H CH₂ 0 3.0279 H CH₃ CH₂O(CO)CH₃CH₃ F CH₂ 0 3.0280 H CH₃ CH₂O(CO)CH₃ CH₃ Cl CH₂ 0 3.0281 H CH₃CH₂O(CO)CH₃ CH₃ H CH₂ 0 3.0282 H CH₃ CH₂OCH₂C≡CH CH₃ F CH₂ 0 3.0283 HCH₃ CH₂OCH₂C≡CH CH₃ Cl CH₂ 0 3.0284 H CH₃ CH₂OCH₂C≡CH CH₃ H CH₂ 0 3.0285H CH₃ CH₂OCH₂C≡CCH₃ CH₃ F CH₂ 0 3.0286 H CH₃ CH₂OCH₂C≡CCH₃ CH₃ Cl CH₂ 03.0287 H CH₃ CH₂OCH₂C≡CCH₃ CH₃ H CH₂ 0 3.0288 H CH₃

CH₃ F CH₂ 0 3.0289 H CH₃

CH₃ Cl CH₂ 0 3.0290 H CH₃

CH₃ H CH₂ 0 3.0291 H CH₃

CH₃ F CH₂ 0 3.0292 H CH₃

CH₃ Cl CH₂ 0 3.0293 H CH₃

CH₃ H CH₂ 0 3.0294 H CH₃

CH₃ F CH₂ 0 3.0295 H CH₃

CH₃ Cl CH₂ 0 3.0296 H CH₃

CH₃ H CH₂ 0 3.0297 H CH₃

CH₃ F CH₂ 0 3.0298 H CH₃

CH₃ Cl CH₂ 0 3.0299 H CH₃

CH₃ H CH₂ 0 3.0300 H CH₃

CH₃ F CH₂ 0 3.0301 H CH₃

CH₃ Cl CH₂ 0 3.0302 H CH₃

CH₃ H CH₂ 0 3.0303 H CH₃

CH₃ F CH₂ 0 3.0304 H CH₃

CH₃ Cl CH₂ 0 3.0305 H CH₃

CH₃ H CH₂ 0 3.0306 H H CH₂OCH₂CH₂OCH₃ CH₃ F CH₂ 1 3.0307 H HCH₂OCH₂CH₂OCH₃ CH₃ Cl CH₂ 1 3.0308 H H CH₂OCH₂CH₂OCH₃ CH₃ H CH₂ 1 3.0309H H CH₂OCH₂CH₂OCH₂CH₃ CH₃ F CH₂ 1 3.0310 H H CH₂OCH₂CH₂OCH₂CH₃ CH₃ ClCH₂ 1 3.0311 H H CH₂OCH₂CH₂OCH₂CH₃ CH₃ H CH₂ 1 3.0312 H HCH₂N(CH₃)SO₂CH₃ CH₃ F CH₂ 1 3.0313 H H CH₂N(CH₃)SO₂CH₃ CH₃ Cl CH₂ 13.0314 H H CH₂N(CH₃)SO₂CH₃ CH₃ H CH₂ 1 3.0315 H H CH₂OCH₂Ph CH₃ F CH₂ 13.0316 H H CH₂OCH₂Ph CH₃ Cl CH₂ 1 3.0317 H H CH₂OCH₂Ph CH₃ H CH₂ 13.0318 H H CH₂OCH₂CH₂OH CH₃ F CH₂ 1 3.0319 H H CH₂OCH₂CH₂OH CH₃ Cl CH₂ 13.0320 H H CH₂OCH₂CH₂OH CH₃ H CH₂ 1 3.0321 H H CH₂OCH₂CH₂Cl CH₃ F CH₂ 13.0322 H H CH₂OCH₂CH₂Cl CH₃ Cl CH₂ 1 3.0323 H H CH₂OCH₂CH₂Cl CH₃ H CH₂ 13.0324 H H CH₂OCH₂CF₃ CH₃ F CH₂ 1 3.0325 H H CH₂OCH₂CF₃ CH₃ Cl CH₂ 13.0326 H H CH₂OCH₂CF₃ CH₃ H CH₂ 1 3.0327 H H CH₂OCH₂CH═CH₂ CH₃ F CH₂ 13.0328 H H CH₂OCH₂CH═CH₂ CH₃ Cl CH₂ 1 3.0329 H H CH₂OCH₂CH═CH₂ CH₃ H CH₂1 3.0330 H H CH₂O(CO)CH₃ CH₃ F CH₂ 1 3.0331 H H CH₂O(CO)CH₃ CH₃ Cl CH₂ 13.0332 H H CH₂O(CO)CH₃ CH₃ H CH₂ 1 3.0333 H H CH₂OCH₂C≡CH CH₃ F CH₂ 13.0334 H H CH₂OCH₂C≡CH CH₃ Cl CH₂ 1 3.0335 H H CH₂OCH₂C≡CH CH₃ H CH₂ 13.0336 H H CH₂OCH₂C≡CCH₃ CH₃ F CH₂ 1 3.0337 H H CH₂OCH₂C≡CCH₃ CH₃ Cl CH₂1 3.0338 H H CH₂OCH₂C≡CCH₃ CH₃ H CH₂ 1 3.0339 H H

CH₃ F CH₂ 1 3.0340 H H

CH₃ Cl CH₂ 1 3.0341 H H

CH₃ H CH₂ 1 3.0342 H H

CH₃ F CH₂ 1 3.0343 H H

CH₃ Cl CH₂ 1 3.0344 H H

CH₃ H CH₂ 1 3.0345 H H

CH₃ F CH₂ 1 3.0346 H H

CH₃ Cl CH₂ 1 3.0347 H H

CH₃ H CH₂ 1 3.0348 H H

CH₃ F CH₂ 1 3.0349 H H

CH₃ Cl CH₂ 1 3.0350 H H

CH₃ H CH₂ 1 3.0351 H H

CH₃ F CH₂ 1 3.0352 H H

CH₃ Cl CH₂ 1 3.0353 H H

CH₃ H CH₂ 1 3.0354 H H

CH₃ F CH₂ 1 3.0355 H H

CH₃ Cl CH₂ 1 3.0356 H H

CH₃ H CH₂ 1 3.0357 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ CH₃ F CH₂ 1 3.0358 CH₃ CH₃CH₂OCH₂CH₂OCH₃ CH₃ Cl CH₂ 1 3.0359 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ CH₃ H CH₂ 13.0360 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ CH₃ F CH₂ 1 3.0361 CH₃ CH₃CH₂OCH₂CH₂OCH₂CH₃ CH₃ Cl CH₂ 1 3.0362 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ CH₃ HCH₂ 1 3.0363 CH₃ CH₃ CH₂N(CH₃)SO₂CH₃ CH₃ F CH₂ 1 3.0364 CH₃ CH₃CH₂N(CH₃)SO₂CH₃ CH₃ Cl CH₂ 1 3.0365 CH₃ CH₃ CH₂N(CH₃)SO₂CH₃ CH₃ H CH₂ 13.0366 CH₃ CH₃ CH₂OCH₂Ph CH₃ F CH₂ 1 3.0367 CH₃ CH₃ CH₂OCH₂Ph CH₃ Cl CH₂1 3.0368 CH₃ CH₃ CH₂OCH₂Ph CH₃ H CH₂ 1 3.0369 CH₃ CH₃ CH₂OCH₂CH₂OH CH₃ FCH₂ 1 3.0370 CH₃ CH₃ CH₂OCH₂CH₂OH CH₃ Cl CH₂ 1 3.0371 CH₃ CH₃CH₂OCH₂CH₂OH CH₃ H CH₂ 1 3.0372 CH₃ CH₃ CH₂OCH₂CH₂Cl CH₃ F CH₂ 1 3.0373CH₃ CH₃ CH₂OCH₂CH₂Cl CH₃ Cl CH₂ 1 3.0374 CH₃ CH₃ CH₂OCH₂CH₂Cl CH₃ H CH₂1 3.0375 CH₃ CH₃ CH₂OCH₂CF₃ CH₃ F CH₂ 1 3.0376 CH₃ CH₃ CH₂OCH₂CF₃ CH₃ ClCH₂ 1 3.0377 CH₃ CH₃ CH₂OCH₂CF₃ CH₃ H CH₂ 1 3.0378 CH₃ CH₃ CH₂OCH₂CH═CH₂CH₃ F CH₂ 1 3.0379 CH₃ CH₃ CH₂OCH₂CH═CH₂ CH₃ Cl CH₂ 1 3.0380 CH₃ CH₃CH₂OCH₂CH═CH₂ CH₃ H CH₂ 1 3.0381 CH₃ CH₃ CH₂O(CO)CH₃ CH₃ F CH₂ 1 3.0382CH₃ CH₃ CH₂O(CO)CH₃ CH₃ Cl CH₂ 1 3.0383 CH₃ CH₃ CH₂O(CO)CH₃ CH₃ H CH₂ 13.0384 CH₃ CH₃ CH₂OCH₂C≡CH CH₃ F CH₂ 1 3.0385 CH₃ CH₃ CH₂OCH₂C≡CH CH₃ ClCH₂ 1 3.0386 CH₃ CH₃ CH₂OCH₂C≡CH CH₃ H CH₂ 1 3.0387 CH₃ CH₃CH₂OCH₂C≡CCH₃ CH₃ F CH₂ 1 3.0388 CH₃ CH₃ CH₂OCH₂C≡CCH₃ CH₃ Cl CH₂ 13.0389 CH₃ CH₃ CH₂OCH₂C≡CCH₃ CH₃ H CH₂ 1 3.0390 CH₃ CH₃

CH₃ F CH₂ 1 3.0391 CH₃ CH₃

CH₃ Cl CH₂ 1 3.0392 CH₃ CH₃

CH₃ H CH₂ 1 3.0393 CH₃ CH₃

CH₃ F CH₂ 1 3.0394 CH₃ CH₃

CH₃ Cl CH₂ 1 3.0395 CH₃ CH₃

CH₃ H CH₂ 1 3.0396 CH₃ CH₃

CH₃ F CH₂ 1 3.0397 CH₃ CH₃

CH₃ Cl CH₂ 1 3.0398 CH₃ CH₃

CH₃ H CH₂ 1 3.0399 CH₃ CH₃

CH₃ F CH₂ 1 3.0400 CH₃ CH₃

CH₃ Cl CH₂ 1 3.0401 CH₃ CH₃

CH₃ H CH₂ 1 3.0402 CH₃ CH₃

CH₃ F CH₂ 1 3.0403 CH₃ CH₃

CH₃ Cl CH₂ 1 3.0404 CH₃ CH₃

CH₃ H CH₂ 1 3.0405 CH₃ CH₃

CH₃ F CH₂ 1 3.0406 CH₃ CH₃

CH₃ Cl CH₂ 1 3.0407 CH₃ CH₃

CH₃ H CH₂ 1 3.0408 H CH₃ CH₂OCH₂CH₂OCH₃ CH₃ F CH₂ 1 3.0409 H CH₃CH₂OCH₂CH₂OCH₃ CH₃ Cl CH₂ 1 3.0410 H CH₃ CH₂OCH₂CH₂OCH₃ CH₃ H CH₂ 13.0411 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ CH₃ F CH₂ 1 3.0412 H CH₃CH₂OCH₂CH₂OCH₂CH₃ CH₃ Cl CH₂ 1 3.0413 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ CH₃ H CH₂1 3.0414 H CH₃ CH₂N(CH₃)SO₂CH₃ CH₃ F CH₂ 1 3.0415 H CH₃ CH₂N(CH₃)SO₂CH₃CH₃ Cl CH₂ 1 3.0416 H CH₃ CH₂N(CH₃)SO₂CH₃ CH₃ H CH₂ 1 3.0417 H CH₃CH₂OCH₂Ph CH₃ F CH₂ 1 3.0418 H CH₃ CH₂OCH₂Ph CH₃ Cl CH₂ 1 3.0419 H CH₃CH₂OCH₂Ph CH₃ H CH₂ 1 3.0420 H CH₃ CH₂OCH₂CH₂OH CH₃ F CH₂ 1 3.0421 H CH₃CH₂OCH₂CH₂OH CH₃ Cl CH₂ 1 3.0422 H CH₃ CH₂OCH₂CH₂OH CH₃ H CH₂ 1 3.0423 HCH₃ CH₂OCH₂CH₂Cl CH₃ F CH₂ 1 3.0424 H CH₃ CH₂OCH₂CH₂Cl CH₃ Cl CH₂ 13.0425 H CH₃ CH₂OCH₂CH₂Cl CH₃ H CH₂ 1 3.0426 H CH₃ CH₂OCH₂CF₃ CH₃ F CH₂1 3.0427 H CH₃ CH₂OCH₂CF₃ CH₃ Cl CH₂ 1 3.0428 H CH₃ CH₂OCH₂CF₃ CH₃ H CH₂1 3.0429 H CH₃ CH₂OCH₂CH═CH₂ CH₃ F CH₂ 1 3.0430 H CH₃ CH₂OCH₂CH═CH₂ CH₃Cl CH₂ 1 3.0431 H CH₃ CH₂OCH₂CH═CH₂ CH₃ H CH₂ 1 3.0432 H CH₃ CH₂O(CO)CH₃CH₃ F CH₂ 1 3.0433 H CH₃ CH₂O(CO)CH₃ CH₃ Cl CH₂ 1 3.0434 H CH₃CH₂O(CO)CH₃ CH₃ H CH₂ 1 3.0435 H CH₃ CH₂OCH₂C≡CH CH₃ F CH₂ 1 3.0436 HCH₃ CH₂OCH₂C≡CH CH₃ Cl CH₂ 1 3.0437 H CH₃ CH₂OCH₂C≡CH CH₃ H CH₂ 1 3.0438H CH₃ CH₂OCH₂C≡CCH₃ CH₃ F CH₂ 1 3.0439 H CH₃ CH₂OCH₂C≡CCH₃ CH₃ Cl CH₂ 13.0440 H CH₃ CH₂OCH₂C≡CCH₃ CH₃ H CH₂ 1 3.0441 H CH₃

CH₃ F CH₂ 1 3.0442 H CH₃

CH₃ Cl CH₂ 1 3.0443 H CH₃

CH₃ H CH₂ 1 3.0444 H CH₃

CH₃ F CH₂ 1 3.0445 H CH₃

CH₃ Cl CH₂ 1 3.0446 H CH₃

CH₃ H CH₂ 1 3.0447 H CH₃

CH₃ F CH₂ 1 3.0448 H CH₃

CH₃ Cl CH₂ 1 3.0449 H CH₃

CH₃ H CH₂ 1 3.0450 H CH₃

CH₃ F CH₂ 1 3.0451 H CH₃

CH₃ Cl CH₂ 1 3.0452 H CH₃

CH₃ H CH₂ 1 3.0453 H CH₃

CH₃ F CH₂ 1 3.0454 H CH₃

CH₃ Cl CH₂ 1 3.0455 H CH₃

CH₃ H CH₂ 1 3.0456 H CH₃

CH₃ F CH₂ 1 3.0457 H CH₃

CH₃ Cl CH₂ 1 3.0458 H CH₃

CH₃ H CH₂ 1

TABLE 4 Intermediates of formulae Da and Db:

No. R₁ R₂ R₃ Y Xa Physical data 4.0001 H H OH CH₂ H see Example P9;tautomeric form Da 4.0002 H H OCH₃ CH₂ H 4.0003 H H OCH₂CH₃ CH₂ H 4.0004H H OC(CH₃)₂ CH₂ H 4.0005 H H OH CH₂CH₂ H see Example P12; tautomericform Da 4.0006 H H OCH₃ CH₂CH₂ H 4.0007 H H OCH₂CH₃ CH₂CH₂ H 4.0008 H HOC(CH₃)₂ CH₂CH₂ H 4.0009 H H OH O H ¹H NMR (300 MHz; CDCl₃) δ 6.35 (s,2H); 5.66 (s, 1H); 3.78 (d, 1H); 3.43 (d, 1H); tautomeric form Da 4.0010H H OCH₃ O H 4.0011 H H OCH₂CH₃ O H 4.0012 H H OC(CH₃)₂ O H 4.0013 H HOH NSO₂CH₃ H 4.0014 H H OCH₃ NSO₂CH₃ H 4.0015 H H OCH₂CH₃ NSO₂CH₃ H4.0016 H H OC(CH₃)₂ NSO₂CH₃ H 4.0017 H H OH NC(O)C(CH₃)₃ H 4.0018 H HOCH₃ NC(O)C(CH₃)₃ H 4.0019 H H OCH₂CH₃ NC(O)C(CH₃)₃ H 4.0020 H HOC(CH₃)₂ NC(O)C(CH₃)₃ H 4.0021 H H OH CH₂ Cl 4.0022 H H OCH₃ CH₂ Cl4.0023 H H OCH₂CH₃ CH₂ Cl 4.0024 H H OC(CH₃)₂ CH₂ Cl 4.0025 H H OHCH₂CH₂ Cl see Preparation Example P11 4.0026 H H OCH₃ CH₂CH₂ Cl 4.0027 HH OCH₂CH₃ CH₂CH₂ Cl 4.0028 H H OC(CH₃)₂ CH₂CH₂ Cl 4.0029 H H OH O Cl4.0030 H H OCH₃ O Cl 4.0031 H H OCH₂CH₃ O Cl 4.0032 H H OC(CH₃)₂ O Cl4.0033 H H OH NSO₂CH₃ Cl 4.0034 H H OCH₃ NSO₂CH₃ Cl 4.0035 H H OCH₂CH₃NSO₂CH₃ Cl 4.0036 H H OC(CH₃)₂ NSO₂CH₃ Cl 4.0037 H H OH NC(O)C(CH₃)₃ Cl4.0038 H H OCH₃ NC(O)C(CH₃)₃ Cl 4.0039 H H OCH₂CH₃ NC(O)C(CH₃)₃ Cl4.0040 H H OC(CH₃)₂ NC(O)C(CH₃)₃ Cl 4.0041 H H OH CH₂ Br 4.0042 H H OCH₃CH₂ Br 4.0043 H H OCH₂CH₃ CH₂ Br 4.0044 H H OC(CH₃)₂ CH₂ Br 4.0045 H HOH CH₂CH₂ Br 4.0046 H H OCH₃ CH₂CH₂ Br 4.0047 H H OCH₂CH₃ CH₂CH₂ Br4.0048 H H OC(CH₃)₂ CH₂CH₂ Br 4.0049 H H OH O Br 4.0050 H H OCH₃ O Br4.0051 H H OCH₂CH₃ O Br 4.0052 H H OC(CH₃)₂ O Br 4.0053 H H OH NSO₂CH₃Br 4.0054 H H OCH₃ NSO₂CH₃ Br 4.0055 H H OCH₂CH₃ NSO₂CH₃ Br 4.0056 H HOC(CH₃)₂ NSO₂CH₃ Br 4.0057 H H OH NC(O)C(CH₃)₃ Br 4.0058 H H OCH₃NC(O)C(CH₃)₃ Br 4.0059 H H OCH₂CH₃ NC(O)C(CH₃)₃ Br 4.0060 H H OC(CH₃)₂NC(O)O(CH₃)₃ Br 4.0061 H CH₃ OH CH₂ H ¹H NMR (300 MHz; CDCl₃) δ 6.30 (m,1H); 6.10 (m, 1H); 3.73 (d, 1H); 3.44 (d, 1H); 1.62 (s, 3H); tautomericform Db 4.0062 H CH₃ OCH₃ CH₂ H 4.0063 H CH₃ OCH₂CH₃ CH₂ H 4.0064 H CH₃OC(CH₃)₂ CH₂ H 4.0065 H CH₃ OH CH₂CH₂ H 4.0066 H CH₃ OCH₃ CH₂CH₂ H4.0067 H CH₃ OCH₂CH₃ CH₂CH₂ H 4.0068 H CH₃ OC(CH₃)₂ CH₂CH₂ H 4.0069 HCH₃ OH O H 4.0070 H CH₃ OCH₃ O H 4.0071 H CH₃ OCH₂CH₃ O H 4.0072 H CH₃OC(CH₃)₂ O H 4.0073 H CH₃ OH NSO₂CH₃ H 4.0074 H CH₃ OCH₃ NSO₂CH₃ H4.0075 H CH₃ OCH₂CH₃ NSO₂CH₃ H 4.0076 H CH₃ OC(CH₃)₂ NSO₂CH₃ H 4.0077 HCH₃ OH NC(O)O(CH₃)₃ H 4.0078 H CH₃ OCH₃ NC(O)O(CH₃)₃ H 4.0079 H CH₃OCH₂CH₃ NC(O)C(CH₃)₃ H 4.0080 H CH₃ OC(CH₃)₂ NC(O)O(CH₃)₃ H 4.0081 H CH₃OH CH₂ Cl 4.0082 H CH₃ OCH₃ CH₂ Cl 4.0083 H CH₃ OCH₂CH₃ CH₂ Cl 4.0084 HCH₃ OC(CH₃)₂ CH₂ Cl 4.0085 H CH₃ OH CH₂CH₂ Cl 4.0086 H CH₃ OCH₃ CH₂CH₂Cl 4.0087 H CH₃ OCH₂CH₃ CH₂CH₂ Cl 4.0088 H CH₃ OC(CH₃)₂ CH₂CH₂ Cl 4.0089H CH₃ OH O Cl 4.0090 H CH₃ OCH₃ O Cl 4.0091 H CH₃ OCH₂CH₃ O Cl 4.0092 HCH₃ OC(CH₃)₂ O Cl 4.0093 H CH₃ OH NSO₂CH₃ Cl 4.0094 H CH₃ OCH₃ NSO₂CH₃Cl 4.0095 H CH₃ OCH₂CH₃ NSO₂CH₃ Cl 4.0096 H CH₃ OC(CH₃)₂ NSO₂CH₃ Cl4.0097 H CH₃ OH NC(O)C(CH₃)₃ Cl 4.0098 H CH₃ OCH₃ NC(O)C(CH₃)₃ Cl 4.0099H CH₃ OCH₂CH₃ NC(O)C(CH₃)₃ Cl 4.0100 H CH₃ OC(CH₃)₂ NC(O)C(CH₃)₃ Cl4.0101 H CH₃ OH CH₂ Br 4.0102 H CH₃ OCH₃ CH₂ Br 4.0103 H CH₃ OCH₂CH₃ CH₂Br 4.0104 H CH₃ OC(CH₃)₂ CH₂ Br 4.0105 H CH₃ OH CH₂CH₂ Br 4.0106 H CH₃OCH₃ CH₂CH₂ Br 4.0107 H CH₃ OCH₂CH₃ CH₂CH₂ Br 4.0108 H CH₃ OC(CH₃)₂CH₂CH₂ Br 4.0109 H CH₃ OH O Br 4.0110 H CH₃ OCH₃ O Br 4.0111 H CH₃OCH₂CH₃ O Br 4.0112 H CH₃ OC(CH₃)₂ O Br 4.0113 H CH₃ OH NSO₂CH₃ Br4.0114 H CH₃ OCH₃ NSO₂CH₃ Br 4.0115 H CH₃ OCH₂CH₃ NSO₂CH₃ Br 4.0116 HCH₃ OC(CH₃)₂ NSO₂CH₃ Br 4.0117 H CH₃ OH NC(O)C(CH₃)₃ Br 4.0118 H CH₃OCH₃ NC(O)O(CH₃)₃ Br 4.0119 H CH₃ OCH₂CH₃ NC(O)O(CH₃)₃ Br 4.0120 H CH₃OC(CH₃)₂ NC(O)C(CH₃)₃ Br 4.0121 CH₃ CH₃ OH CH₂ H 4.0122 CH₃ CH₃ OCH₃ CH₂H 4.0123 CH₃ CH₃ OCH₂CH₃ CH₂ H 4.0124 CH₃ CH₃ OC(CH₃)₂ CH₂ H 4.0125 CH₃CH₃ OH CH₂CH₂ H 4.0126 CH₃ CH₃ OCH₃ CH₂CH₂ H 4.0127 CH₃ CH₃ OCH₂CH₃CH₂CH₂ H 4.0128 CH₃ CH₃ OC(CH₃)₂ CH₂CH₂ H 4.0129 CH₃ CH₃ OH O H 4.0130CH₃ CH₃ OCH₃ O H 4.0131 CH₃ CH₃ OCH₂CH₃ O H 4.0132 CH₃ CH₃ OC(CH₃)₂ O H4.0133 CH₃ CH₃ OH NSO₂CH₃ H 4.0134 CH₃ CH₃ OCH₃ NSO₂CH₃ H 4.0135 CH₃ CH₃OCH₂CH₃ NSO₂CH₃ H 4.0136 CH₃ CH₃ OC(CH₃)₂ NSO₂CH₃ H 4.0137 CH₃ CH₃ OHNC(O)O(CH₃)₃ H 4.0138 CH₃ CH₃ OCH₃ NC(O)C(CH₃)₃ H 4.0139 CH₃ CH₃ OCH₂CH₃NC(O)O(CH₃)₃ H 4.0140 CH₃ CH₃ OC(CH₃)₂ NC(O)C(CH₃)₃ H 4.0141 CH₃ CH₃ OHCH₂ Cl 4.0142 CH₃ CH₃ OCH₃ CH₂ Cl see Preparation Example P3 4.0143 CH₃CH₃ OCH₂CH₃ CH₂ Cl 4.0144 CH₃ CH₃ OC(CH₃)₂ CH₂ Cl 4.0145 CH₃ CH₃ OHCH₂CH₂ Cl 4.0146 CH₃ CH₃ OCH₃ CH₂CH₂ Cl 4.0147 CH₃ CH₃ OCH₂CH₃ CH₂CH₂ Cl4.0148 CH₃ CH₃ OC(CH₃)₂ CH₂CH₂ Cl 4.0149 CH₃ CH₃ OH O Cl 4.0150 CH₃ CH₃OCH₃ O Cl 4.0151 CH₃ CH₃ OCH₂CH₃ O Cl 4.0152 CH₃ CH₃ OC(CH₃)₂ O Cl4.0153 CH₃ CH₃ OH NSO₂CH₃ Cl 4.0154 CH₃ CH₃ OCH₃ NSO₂CH₃ Cl 4.0155 CH₃CH₃ OCH₂CH₃ NSO₂CH₃ Cl 4.0156 CH₃ CH₃ OC(CH₃)₂ NSO₂CH₃ Cl 4.0157 CH₃ CH₃OH NO(O)O(CH₃)₃ Cl 4.0158 CH₃ CH₃ OCH₃ NC(O)C(CH₃)₃ Cl 4.0159 CH₃ CH₃OCH₂CH₃ NC(O)C(CH₃)₃ Cl 4.0160 CH₃ CH₃ OC(CH₃)₂ NC(O)C(CH₃)₃ Cl 4.0161CH₃ CH₃ OH CH₂ Br 4.0162 CH₃ CH₃ OCH₃ CH₂ Br 4.0163 CH₃ CH₃ OCH₂CH₃ CH₂Br 4.0164 CH₃ CH₃ OC(CH₃)₂ CH₂ Br 4.0165 CH₃ CH₃ OH CH₂CH₂ Br 4.0166 CH₃CH₃ OCH₃ CH₂CH₂ Br 4.0167 CH₃ CH₃ OCH₂CH₃ CH₂CH₂ Br 4.0168 CH₃ CH₃OC(CH₃)₂ CH₂CH₂ Br 4.0169 CH₃ CH₃ OH O Br 4.0170 CH₃ CH₃ OCH₃ O Br4.0171 CH₃ CH₃ OCH₂CH₃ O Br 4.0172 CH₃ CH₃ OC(CH₃)₂ O Br see PreparationExample P6 4.0173 CH₃ CH₃ OH NSO₂CH₃ Br 4.0174 CH₃ CH₃ OCH₃ NSO₂CH₃ Br4.0175 CH₃ CH₃ OCH₂CH₃ NSO₂CH₃ Br 4.0176 CH₃ CH₃ OC(CH₃)₂ NSO₂CH₃ Br4.0177 CH₃ CH₃ OH NC(O)O(CH₃)₃ Br 4.0178 CH₃ CH₃ OCH₃ NC(O)O(CH₃)₃ Br4.0179 CH₃ CH₃ OCH₂CH₃ NC(O)C(CH₃)₃ Br 4.0180 CH₃ CH₃ OC(CH₃)₂NC(O)C(CH₃)₃ Br 4.0181 H H OH

H ¹H NMR (300 MHz; CDCl₃) δ 6.30 (sxm, 2H); 3.60 (d, 1H); 3.23 (d, 1H);2.82 (s, 1H); 0.75 (m, 4H); tautomeric form Db 4.0182 H H OH C(═C(CH₃)₂)H ¹H NMR (300 MHz; CDCl₃) δ 6.82 (sxm, 2H); 4.14 (sxm, 2H); 3.60 (d,1H); 3.13 (d, 1H); 1.75 (s, 6H); tautomeric form Db 4.0183 H H OHCH₂CH(COOCH₃) H R₇ = Br, see Preparation Example P13 4.0184 H H OHCH₂CH(COOCH₃) H R₇ = CH

TABLE 5 Intermediates of formulae VII: (VII)

No. R₁ R₂ R₃ R₄ Y Xa Physical data 5.0000 H H OCH₃ OCH₃ CH₂ H 5.0001 H HOCH₂CH₃ OCH₂CH₃ CH₂ H 5.0002 H H —OCH₂CH₂O— CH₂ H see Example P8 5.0003H H OCH₃ OCH₃ O H 5.0004 H H OCH₂CH₃ OCH₂CH₃ O H 5.0005 H H —OCH₂CH₂O— OH 5.0006 H H OCH₃ OCH₃ NSO₂CH₃ H 5.0007 H H OCH₂CH₃ OCH₂CH₃ NSO₂CH₃ H5.0008 H H —OCH₂CH₂O— NSO₂CH₃ H 5.0009 H H OCH₃ OCH₃ NC(O)C(CH₃)₃ H5.0010 H H OCH₂CH₃ OCH₂CH₃ NC(O)C(CH₃)₃ H 5.0011 H H —OCH₂CH₂O—NC(O)C(CH₃)₃ H 5.0012 H H OCH₃ OCH₃ CH₂CH₂ H 5.0013 H H OCH₂CH₃ OCH₂CH₃CH₂CH₂ H 5.0014 H H —OCH₂CH₂O— CH₂CH₂ H 5.0015 H H OCH₃ OCH₃ CH₂ Cl5.0016 H H OCH₂CH₃ OCH₂CH₃ CH₂ Cl 5.0017 H H —OCH₂CH₂O— CH₂ Cl 5.0018 HH OCH₃ OCH₃ O Cl 5.0019 H H OCH₂CH₃ OCH₂CH₃ O Cl 5.0020 H H —OCH₂CH₂O— OCl 5.0021 H H OCH₃ OCH₃ NSO₂CH₃ Cl 5.0022 H H OCH₂CH₃ OCH₂CH₃ NSO₂CH₃ Cl5.0023 H H —OCH₂CH₂O— NSO₂CH₃ Cl 5.0024 H H OCH₃ OCH₃ NC(O)C(CH₃)₃ Cl5.0025 H H OCH₂CH₃ OCH₂CH₃ NC(O)C(CH₃)₃ Cl 5.0026 H H —OCH₂CH₂O—NC(O)C(CH₃)₃ Cl 5.0027 H H OCH₃ OCH₃ CH₂CH₂ Cl 5.0028 H H OCH₂CH₃OCH₂CH₃ CH₂CH₂ Cl 5.0029 H H —OCH₂CH₂O— CH₂CH₂ Cl 5.0030 H H OCH₃ OCH₃CH₂ Br 5.0031 H H OCH₂CH₃ OCH₂CH₃ CH₂ Br 5.0032 H H —OCH₂CH₂O— CH₂ Br5.0033 H H OCH₃ OCH₃ O Br 5.0034 H H OCH₂CH₃ OCH₂CH₃ O Br 5.0035 H H—OCH₂CH₂O— O Br 5.0036 H H OCH₃ OCH₃ NSO₂CH₃ Br 5.0037 H H OCH₂CH₃OCH₂CH₃ NSO₂CH₃ Br 5.0038 H H —OCH₂CH₂O— NSO₂CH₃ Br 5.0039 H H OCH₃ OCH₃NC(O)C(CH₃)₃ Br 5.0040 H H OCH₂CH₃ OCH₂CH₃ NC(O)C(CH₃)₃ Br 5.0041 H H—OCH₂CH₂O— NC(O)C(CH₃)₃ Br 5.0042 H H OCH₃ OCH₃ CH₂CH₂ Br 5.0043 H HOCH₂CH₃ OCH₂CH₃ CH₂CH₂ Br 5.0044 H H —OCH₂CH₂O— CH₂CH₂ Br 5.0045 H CH₃OCH₃ OCH₃ CH₂ H 5.0046 H CH₃ OCH₂CH₃ OCH₂CH₃ CH₂ H 5.0047 H CH₃—OCH₂CH₂O— CH₂ H 5.0048 H CH₃ OCH₃ OCH₃ O H 5.0049 H CH₃ OCH₂CH₃ OCH₂CH₃O H 5.0050 H CH₃ —OCH₂CH₂O— O H 5.0051 H CH₃ OCH₃ OCH₃ NSO₂CH₃ H 5.0052H CH₃ OCH₂CH₃ OCH₂CH₃ NSO₂CH₃ H 5.0053 H CH₃ —OCH₂CH₂O— NSO₂CH₃ H 5.0054H CH₃ OCH₃ OCH₃ NC(O)O(CH₃)₃ H 5.0055 H CH₃ OCH₂CH₃ OCH₂CH₃ NC(O)C(CH₃)₃H 5.0056 H CH₃ —OCH₂CH₂O— NC(O)C(CH₃)₃ H 5.0057 H CH₃ OCH₃ OCH₃ CH₂CH₂ H5.0058 H CH₃ OCH₂CH₃ OCH₂CH₃ CH₂CH₂ H 5.0059 H CH₃ —OCH₂CH₂O— CH₂CH₂ H5.0060 H CH₃ OCH₃ OCH₃ CH₂ Cl 5.0061 H CH₃ OCH₂CH₃ OCH₂CH₃ CH₂ Cl 5.0062H CH₃ —OCH₂CH₂O— CH₂ Cl 5.0063 H CH₃ OCH₃ OCH₃ O Cl 5.0064 H CH₃ OCH₂CH₃OCH₂CH₃ O Cl 5.0065 H CH₃ —OCH₂CH₂O— O Cl 5.0066 H CH₃ OCH₃ OCH₃ NSO₂CH₃Cl 5.0067 H CH₃ OCH₂CH₃ OCH₂CH₃ NSO₂CH₃ Cl 5.0068 H CH₃ —OCH₂CH₂O—NSO₂CH₃ Cl 5.0069 H CH₃ OCH₃ OCH₃ NC(O)C(CH₃)₃ Cl 5.0070 H CH₃ OCH₂CH₃OCH₂CH₃ NC(O)C(CH₃)₃ Cl 5.0071 H CH₃ —OCH₂CH₂O— NC(O)C(CH₃)₃ Cl 5.0072 HCH₃ OCH₃ OCH₃ CH₂CH₂ Cl 5.0073 H CH₃ OCH₂CH₃ OCH₂CH₃ CH₂CH₂ Cl 5.0074 HCH₃ —OCH₂CH₂O— CH₂CH₂ Cl 5.0075 H CH₃ OCH₃ OCH₃ CH₂ Br 5.0076 H CH₃OCH₂CH₃ OCH₂CH₃ CH₂ Br 5.0077 H CH₃ —OCH₂CH₂O— CH₂ Br 5.0078 H CH₃ OCH₃OCH₃ O Br 5.0079 H CH₃ OCH₂CH₃ OCH₂CH₃ O Br 5.0080 H CH₃ —OCH₂CH₂O— O Br5.0081 H CH₃ OCH₃ OCH₃ NSO₂CH₃ Br 5.0082 H CH₃ OCH₂CH₃ OCH₂CH₃ NSO₂CH₃Br 5.0083 H CH₃ —OCH₂CH₂O— NSO₂CH₃ Br 5.0084 H CH₃ OCH₃ OCH₃NC(O)O(CH₃)₃ Br 5.0085 H CH₃ OCH₂CH₃ OCH₂CH₃ NC(O)C(CH₃)₃ Br 5.0086 HCH₃ —OCH₂CH₂O— NC(O)O(CH₃)₃ Br 5.0087 H CH₃ OCH₃ OCH₃ CH₂CH₂ Br 5.0088 HCH₃ OCH₂CH₃ OCH₂CH₃ CH₂CH₂ Br 5.0089 H CH₃ —OCH₂CH₂O— CH₂CH₂ Br 5.0090CH₃ CH₃ OCH₃ OCH₃ CH₂ H 5.0091 CH₃ CH₃ OCH₂CH₃ OCH₂CH₃ CH₂ H 5.0092 CH₃CH₃ —OCH₂CH₂O— CH₂ H 5.0093 CH₃ CH₃ OCH₃ OCH₃ O H see Example P5 5.0094CH₃ CH₃ OCH₂CH₃ OCH₂CH₃ O H 5.0095 CH₃ CH₃ —OCH₂CH₂O— O H 5.0096 CH₃ CH₃OCH₃ OCH₃ NSO₂CH₃ H 5.0097 CH₃ CH₃ OCH₂CH₃ OCH₂CH₃ NSO₂CH₃ H 5.0098 CH₃CH₃ —OCH₂CH₂O— NSO₂CH₃ H 5.0099 CH₃ CH₃ OCH₃ OCH₃ NC(O)O(CH₃)₃ H 5.0100CH₃ CH₃ OCH₂CH₃ OCH₂CH₃ NC(O)O(CH₃)₃ H 5.0101 CH₃ CH₃ —OCH₂CH₂O—NC(O)O(CH₃)₃ H 5.0102 CH₃ CH₃ OCH₃ OCH₃ CH₂CH₂ H 5.0103 CH₃ CH₃ OCH₂CH₃OCH₂CH₃ CH₂CH₂ H 5.0104 CH₃ CH₃ —OCH₂CH₂O— CH₂CH₂ H 5.0105 CH₃ CH₃ OCH₃OCH₃ CH₂ Cl 5.0106 CH₃ CH₃ OCH₂CH₃ OCH₂CH₃ CH₂ Cl 5.0107 CH₃ CH₃—OCH₂CH₂O— CH₂ Cl 5.0108 CH₃ CH₃ OCH₃ OCH₃ O Cl see Example P3 5.0109CH₃ CH₃ OCH₂CH₃ OCH₂CH₃ O Cl 5.0110 CH₃ CH₃ —OCH₂CH₂O— O Cl 5.0111 CH₃CH₃ OCH₃ OCH₃ NSO₂CH₃ Cl 5.0112 CH₃ CH₃ OCH₂CH₃ OCH₂CH₃ NSO₂CH₃ Cl5.0113 CH₃ CH₃ —OCH₂CH₂O— NSO₂CH₃ Cl 5.0114 CH₃ CH₃ OCH₃ OCH₃NC(O)O(CH₃)₃ Cl 5.0115 CH₃ CH₃ OCH₂CH₃ OCH₂CH₃ NC(O)O(CH₃)₃ Cl 5.0116CH₃ CH₃ —OCH₂CH₂O— NC(O)O(CH₃)₃ Cl 5.0117 CH₃ CH₃ OCH₃ OCH₃ CH₂CH₂ Cl5.0118 CH₃ CH₃ OCH₂CH₃ OCH₂CH₃ CH₂CH₂ Cl 5.0119 CH₃ CH₃ —OCH₂CH₂O—CH₂CH₂ Cl 5.0120 CH₃ CH₃ OCH₃ OCH₃ CH₂ Br 5.0121 CH₃ CH₃ OCH₂CH₃ OCH₂CH₃CH₂ Br 5.0122 CH₃ CH₃ —OCH₂CH₂O— CH₂ Br 5.0123 CH₃ CH₃ OCH₃ OCH₃ O Br5.0124 CH₃ CH₃ OCH₂CH₃ OCH₂CH₃ O Br 5.0125 CH₃ CH₃ —OCH₂CH₂O— O Br5.0126 CH₃ CH₃ OCH₃ OCH₃ NSO₂CH₃ Br 5.0127 CH₃ CH₃ OCH₂CH₃ OCH₂CH₃NSO₂CH₃ Br 5.0128 CH₃ CH₃ —OCH₂CH₂O— NSO₂CH₃ Br 5.0129 CH₃ CH₃ OCH₃ OCH₃NC(O)C(CH₃)₃ Br 5.0130 CH₃ CH₃ OCH₂CH₃ OCH₂CH₃ NC(O)O(CH₃)₃ Br 5.0131CH₃ CH₃ —OCH₂CH₂O— NC(O)C(CH₃)₃ Br 5.0132 CH₃ CH₃ OCH₃ OCH₃ CH₂CH₂ Br5.0133 CH₃ CH₃ OCH₂CH₃ OCH₂CH₃ CH₂CH₂ Br 5.0134 CH₃ CH₃ —OCH₂CH₂O—CH₂CH₂ Br 5.0135 H H —OCH₂CH₂O—

Cl Amorphous crystals

TABLE 6 Intermediates of formula VI: (VI)

No. A₁ A₂ R₁ R₂ Y Xa Physical data 6.0000 CH CH H H C(═CH(OAc)) Cl majorisomer I: ¹H NMR (300 MHz: CDCl₃) δ 7.12 (s, 1H); 6.77 (dxd, 1H); 6.35(dxd, 1H); 4.02 (d, 1H); 3.95 (d, 1H); 2.18 (s, 3H). 6.0001 CH CH H HC(═CH(OAc)) Cl minor isomer II: ¹H NMR (300 MHz; CDCl₃) δ 7.14 (s, 1H);6.84 (dxd, 1H); 6.29 (dxd, 1H); 4.55 (d, 1H); 3.54 (d, 1H); 2.19 (s,3H).

BIOLOGICAL EXAMPLES Example B1 Herbicidal Action Prior to Emergence ofthe Plants (Pre-Emergence Action)

Monocotyledonous and dicotyledonous test plants are sown in standardsoil in plastic pots. Immediately after sowing, the test compounds, inthe form of an aqueous suspension (prepared from a 25% wettable powder(Example F3, b) according to WO 97/34485) or in the form of an emulsion(prepared from a 25% emulsifiable concentrate (Example F1, c)), areapplied by spraying in a concentration corresponding to 125 g or 250 gof active ingredient/ha (500 liters of water/ha). The test plants arethen grown in a greenhouse under optimum conditions. After a testduration of 3 weeks, the test is evaluated in accordance with a scale often ratings (10=total damage, 0=no action). Ratings of from 10 to 6(especially from 10 to 8) indicate good to very good herbicidal action.The compounds of formula I exhibit strong herbicidal action in thistest. Examples of the good herbicidal action of the compounds are givenin Table B1:

TABLE B1 Pre-emergence herbicidal action: Ex. No. gr/ha PanicumEchinochloa Abutilon Amaranthus Chenopodium Kochia 1.0301 250 7 7 7 8 98 1.0411 250 10 9 10 10 10 10

Example B2 Post-Emergence Herbicidal Action

In a greenhouse, monocotyledonous and dicotyledonous test plants aregrown in standard soil in plastic pots and at the 4- to 6-leaf stage aresprayed with an aqueous suspension of the test compounds of formula Iprepared from a 25% wettable powder (Example F3, b) according to WO97/34485) or with an emulsion of the test compounds of formula Iprepared from a 25% emulsifiable concentrate (Example F1, c) accordingto WO 97/34485), in a concentration corresponding to 125 g or 250 g ofactive ingredient/ha (500 liters of water/ha). The test plants are thengrown on in a greenhouse under optimum conditions. After a test durationof about 18 days, the test is evaluated in accordance with a scale often ratings (10=total damage, 0=no action). Ratings of from 10 to 6(especially from 10 to 7) indicate good to very good herbicidal action.The compounds of formula I exhibit a strong herbicidal action in thistest. Examples of the good herbicidal action of the compounds are givenin Table B2:

TABLE B2 Post-emergence herbicidal action: Ex. No. gr/ha Abutilon IpomeaAmaranthus Chenopodium Stellaria Abutilon 1.0301 250 9 8 8 8 8 8 1.0411250 9 10 9 10 9 9 1.1153 250 7 8 7 8 10 8

Example B3 Comparison Test with a Compound from the Prior Art:Post-Emergence Herbicidal Action

The post-emergence herbicidal action of compound No. 1.0411 according tothe invention is compared with compound “A” from WO 01/94339:

TABLE B3 Post-emergence action: Ex. No. gr/ha Brachiaria Rottboelia SidaPolygonum Sinapis Galium 1.0411 15 10 3 8 8 8 6 A 15 4 0 7 5 6 5

It can be seen from Table B3 that compound No. 1.0411 according to theinvention at a rate of application of 15 g/ha exhibits considerablybetter herbicidal action on the weeds than compound “A” from the priorart. This enhanced action was not to be expected in view of thestructural similarity of the compounds.

1. A compound of formula I

wherein Y is oxygen, NR_(4a), sulfur, sulfonyl, sulfinyl, C(O),C(═NR_(4b)), C(═CR_(6a)R_(6b)) or a C₁-C₄alkylene or C₂-C₄alkenylenechain, which may be interrupted by oxygen, NR_(5a), sulfur, sulfonyl,sulfinyl, C(O) or C(═NR_(5b)) and/or mono- or poly-substituted by R₆; A₁is nitrogen or CR₇; A₂ is nitrogen or CR₈; R₁, R₂, R₆, R₇ and R₈ areeach independently of the others hydrogen, hydroxy, mercapto, NO₂,cyano, halogen, formyl, oxyiminomethylene, C₁-C₆alkoxyiminomethylene,C₁-C₆alkyl, C₁-C₆haloalkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl,C₂-C₆alkynyl, C₂-C₆haloalkynyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy,C₃-C₆alkenyloxy, C₃-C₆alkynyloxy, C₃-C₆oxacycloalkyl,C₃-C₆thiacycloalkyl, C₃-C₆dioxacycloalkyl, C₃-C₆dithiacycloalkyl,C₃-C₆oxathiacycloalkyl, C₁-C₆alkoxycarbonyl, C₁-C₆alkylcarbonyl,C₁-C₆alkoxycarbonyloxy, C₁-C₆alkylcarbonyloxy, C₁-C₆alkylthio,C₁-C₆-alkylsulfonyl, C₁-C₆alkylsulfinyl, NR₉R₁₀, C₃-C₆cycloalkyl,tri(C₁-C₆alkyl)silyl, di(C₁-C₆alkyl)-phenylsilyl,tri(C₁-C₆alkyl)silyloxy, di(C₁-C₆alkyl)phenylsilyloxy or Ar₁; or R₁, R₂,R₆, R₇, R₈ are each independently of the others a C₁-C₆alkyl,C₂-C₆alkenyl, C₂-C₆alkynyl or C₃-C₆cycloalkyl group, which may beinterrupted by oxygen, sulfur, sulfonyl, sulfinyl, —NR₁₁— or —C(O)—and/or mono-, di- or tri-substituted by hydroxy, mercapto, NO₂, cyano,halogen, formyl, C₁-C₆alkoxy, C₃-C₆alkenyloxy, C₃-C₆alkynyloxy,C₁-C₆haloalkoxy, C₁-C₂alkoxy-C₁-C₂alkoxy, C₁-C₄alkoxycarbonyloxy,C₁-C₄alkylcarbonyloxy, C₁-C₄alkoxycarbonyl, C₁-C₄alkylcarbonyl,C₁-C₆alkylthio, C₁-C₆alkylsulfinyl, C₁-C₆alkylsulfonyl, NR₁₂R₁₃,C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl, C₃-C₆cycloalkyl,tri(C₁-C₆alkyl)silyl, tri(C₁-C₆alkyl)silyloxy or Ar₂; or twosubstituents R₆ at the same carbon atom together form a —CH₂O— or aC₂-C₅alkylene chain, which may be interrupted once or twice by oxygen,sulfur, sulfinyl or sulfonyl and/or mono- or poly-substituted by R_(6c),with the proviso that two hetero atoms may not be located next to oneanother; or two substituents R₆ at different carbon atoms together forman oxygen bridge or a C₁-C₄alkylene chain, which may in turn besubstituted by R_(6c); or R₇ and R₈ together form a —CH₂CH═CH—, —OCH═CH—or —CH═CH—CH═CH— bridge or a C₃-C₄alkylene chain, which may beinterrupted by oxygen or —S(O)_(n1)— and/or mono- or poly-substituted byR_(6d); R₃ is hydroxy, halogen, mercapto, C₁-C₈alkylthio,C₁-C₈alkylsulfinyl, C₁-C₈alkylsulfonyl, C₁-C₈haloalkylthio,C₁-C₈haloalkylsulfinyl, C₁-C₈haloalkylsulfonyl,C₁-C₄alkoxy-C₁-C₄alkylthio, C₁-C₄alkoxy-C₁-C₄alkylsulfinyl,C₁-C₄alkoxy-C₁-C₄alkylsulfonyl, C₃-C₈alkenylthio, C₃-C₈-alkynylthio,C₁-C₄alkylthio-C₁-C₄alkylthio, C₃-C₄alkenylthio-C₁-C₄alkylthio,C₁-C₄alkoxycarbonyl-C₁-C₄alkylthio,C₁-C₄alkoxycarbonyl-C₁-C₄alkylsulfinyl,C₁-C₄alkoxycarbonyl-C₁-C₄alkylsulfonyl, C₃-C₈cycloalkylthio,C₃-C₈cycloalkylsulfinyl, C₃-C₈cycloalkylsulfonyl, phenyl-C₁-C₄alkylthio,phenyl-C₁-C₄alkylsulfinyl, phenyl-C₁-C₄alkylsulfonyl, S(O)n₁—Ar₃,phenylthio, phenylsulfinyl, phenylsulfonyl, it being possible for thephenyl-containing groups to be substituted by one or more C₁-C₃alkyl,C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₄alkoxycarbonyl,halogen, cyano, hydroxy or nitro groups; or R₃ is O⁻M⁺, wherein M⁺ is analkali metal cation or an ammonium cation; Q is a radical

p₁, p₂ and p₃ are 0 or 1; m₁, m₂ and m₃ are 1, 2 or 3; X₁, X₂ and X₃ arehydroxy, halogen, C₁-C₆alkyl, C₁-C₆haloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl, C₂-C₆alkynyl, C₂-C₆haloalkynyl, C₁-C₆alkoxy,C₁-C₆haloalkoxy, C₁-C₆alkylthio, C₁-C₆alkylsulfinyl, C₁-C₆alkylsulfonyl,C₁-C₆haloalkylthio, C₁-C₆haloalkylsulfinyl or C₁-C₆haloalkylsulfonyl;Z₁, Z₂ and Z₃ are C₁-C₆alkyl which is substituted by the followingsubstituents: C₃-C₄cycloalkyl or C₃-C₄cycloalkyl substituted by halogen,C₁-C₆alkyl, C₁-C₃alkoxy or C₁-C₃alkoxy-C₁-C₃alkyl; oxiranyl or oxiranylsubstituted by C₁-C₆alkyl or C₁-C₃alkoxy-C₁-C₃alkyl; 3-oxetanyl or3-oxetanyl substituted by C₁-C₆alkyl, C₁-C₃alkoxy orC₁-C₃alkoxy-C₁-C₃alkyl; 3-oxetanyloxy or 3-oxetanyloxy substituted byC₁-C₆alkyl, C₁-C₃alkoxy or C₁-C₃alkoxy-C₁-C₃-alkyl; C₃-C₆cycloalkyloxyor C₃-C₄cycloalkyloxy substituted by halogen, C₁-C₆alkyl, C₁-C₃-alkoxyor C₁-C₃alkoxy-C₁-C₃alkyl; C₁-C₆haloalkoxy; C₁-C₆alkylsulfonyloxy;C₁-C₆haloalkylsulfonyloxy; phenylsulfonyloxy; benzylsulfonyloxy,benzoyloxy; phenoxy; phenylthio; phenyl-sulfinyl; phenylsulfonyl; Ar₁₀;OAr₁₂; tri(C₁-C₆alkyl)silyl or tri(C₁-C₆alkyl)silyloxy, it beingpossible for the phenyl-containing groups to be mono- orpoly-substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy,C₁-C₃haloalkoxy, halogen, cyano, hydroxy or nitro; or Z₁, Z₂ and Z₃ are3-oxetanyl; 3-oxetanyl substituted by C₁-C₃alkoxy,C₁-C₃alkoxy-C₁-C₃alkyl or C₁-C₆alkyl; C₃-C₆cycloalkyl substituted byhalogen, C₁-C₃alkyl or C₁-C₃alkoxy-C₁-C₃alkyl; tri(C₁-C₆alkyl)silyl;tri(C₁-C₆alkyl)silyloxy or CH═P(phenyl)₃; or Z₁, Z₂ and Z₃ are aC₁-C₆alkyl, C₂-C₆alkenyl or C₂-C₆alkynyl group, which is interrupted byoxygen, —O(CO)—, —(CO)O—, —O(CO)O—, —N(R₁₄)O—, —ONR₁₅—, sulfur,sulfinyl, sulfonyl,—SO₂NR₁₆—, —NR₁₇SO₂— or —NR₁₈— and is mono- orpoly-substituted by L₁; it also being possible for L₁ to be bonded atthe terminal carbon atom of the C₁-C₆alkyl, C₂-C₆alkenyl or C₂-C₆alkynylgroup; or Z₁, Z₂ and Z₃ are hydrogen, hydroxy, mercapto, NO₂, cyano,halogen, formyl, C₁-C₆alkyl, C₁-C₆haloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl, C₂-C₆alkynyl, C₂-C₆haloalkynyl, C₁-C₆alkoxy,C₁-C₆haloalkoxy, C₁-C₆alkoxycarbonyl, C₁-C₆alkylcarbonyl,C₁-C₆alkylthio, C₁-C₆alkylsulfonyl, C₁-C₆alkylsulfinyl, NR₂₂R₂₃, phenylwhich may be mono- or poly-substituted by C₁-C₃alkyl, C₁-C₃haloalkyl,C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano, hydroxy or nitro,C₃-C₆cycloalkyl, C₅-C₆cycloalkyl substituted by C₁-C₃alkoxy,C₁-C₃alkoxy-C₁-C₃alkyl or C₁-C₆alkyl, or Ar₅, O—Ar₆, N(R₂₄)Ar₇ orS(O)n₆Ar₈; L₁ is hydrogen, halogen, hydroxy, amino, formyl, nitro,cyano, mercapto, carbamoyl, P(O)(OC₁—C₆alkyl)₂, C₁-C₆alkoxy,C₁-C₆haloalkoxy, C₁-C₆alkoxycarbonyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl,C₂-C₆alkynyl, C₂-C₆haloalkynyl, C₃-C₆cycloalkyl, halo-substitutedC₃-C₆cycloalkyl, C₃-C₆alkenyloxy, C₃-C₆alkynyloxy, C₃-C₆haloalkenyloxy,cyano-C₁-C₆alkoxy, C₁-C₆alkoxy-C₁-C₆alkoxy, C₁-C₆alkylthio-C₁-C₆alkoxy,C₁-C₆alkylsulfinyl-C₁-C₆alkoxy, C₁-C₆-alkylsulfonyl-C₁-C₆alkoxy,C₁-C₆alkoxycarbonyl-C₁-C₆alkoxy,C₁-C₆alkylcarbonyloxy-C₁-C₆-alkylcarbonyl, C₁-C₆alkylthio,C₁-C₆alkylsulfinyl, C₁-C₆alkylsulfonyl, C₁-C₆haloalkylthio,C₁-C₆haloalkylsulfinyl, C₁-C₆haloalkylsulfonyl or oxiranyl, which may inturn be substituted by C₁-C₆alkyl, C₁-C₃alkoxy orC₁-C₃alkoxy-C₁-C₃alkyl, or (3-oxetanyl)-oxy, which may in turn besubstituted by C₁-C₆alkyl, C₁-C₃alkoxy or C₁-C₃alkoxy-C₁-C₃alkyl, orbenzoyloxy, benzyloxy, benzylthio, benzylsulfinyl, benzylsulfonyl,C₁-C₆alkylamino, di(C₁-C₆alkyl)amino, R₁₉S(O)₂O—, R₂₀N(R₂₁)SO₂—,rhodano, phenyl, phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl,Ar₄ or OAr₁₁, it being possible for the phenyl-containing groups in turnto be substituted by one or more C₁-C₃alkyl, C₁-C₃haloalkyl,C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano, hydroxy or nitro groups;R_(4a) and R_(5a) are each independently of the other hydrogen,C₁-C₆alkyl, C₁-C₆haloalkyl, cyano, formyl, C₁-C₆alkylcarbonyl,C₁-C₆alkoxycarbonyl, carbamoyl, C₁-C₆alkylaminocarbonyl,di(C₁-C₆alkylamino)carbonyl, di(C₁-C₆alkylamino)sulfonyl,C₃-C₆cycloalkylcarbonyl, C₁-C₆-alkylsulfonyl, phenylcarbonyl,phenylaminocarbonyl or phenylsulfonyl, it being possible for the phenylgroups to be mono- or poly-substituted by C₁-C₆alkyl, C₁-C₆haloalkyl,C₁-C₆alkoxy, C₁-C₆haloalkoxy, halogen, cyano, hydroxy or nitro; R_(4b)and R_(5b) are each independently of the other hydroxy, C₁-C₆alkoxy,C₃-C₆alkenyloxy, C₃-C₆alkynyloxy or benzyloxy, it being possible for thebenzyl group to be mono- or poly-substituted by C₁-C₆alkyl,C₁-C₆haloalkyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, halogen, cyano, hydroxy ornitro; R₉, R₁₁, R₁₃, R₁₆, R₁₇, R₁₈, R₂₀, R₂₃ and R₂₄ are eachindependently of the others hydrogen, C₁-C₆alkyl, Ar₉, C₁-C₆haloalkyl,C₁-C₆alkylcarbonyl, C₁-C₆alkoxycarbonyl, C₁-C₆alkylsulfonyl, phenyl, itbeing possible for the phenyl group in turn to be mono- orpoly-substituted by C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxy,C₁-C₆haloalkoxy, halogen, cyano, hydroxy or nitro; R_(6a) is hydrogen,C₁-C₆alkyl or C₁-C₆alkylcarbonyl; or together with R_(6b) is aC₂-C₅alkylene chain; R_(6b), R_(6d), R₁₀, R₁₂ and R₂₂ are eachindependently of the others hydrogen or C₁-C₆alkyl; R_(6c), R₁₄, R₁₅,R₁₉ and R₂₁ are each independently of the others C₁-C₆alkyl orC₁-C₆haloalkyl; Ar₁, Ar₂, Ar₃, Ar₄, Ar₅, Ar₆, Ar₇, Ar₈, Ar₉, Ar₁₀, Ar₁₁and Ar₁₂ are each independently of the others a five- to ten-membered,monocyclic or fused bicyclic ring system, which may be aromatic,partially saturated or fully saturated and may contain from 1 to 4hetero atoms selected from nitrogen, oxygen, sulfur, C(O) and C(═NR₂₅),and each ring system may contain not more than two oxygen atoms, notmore than two sulfur atoms, not more than two C(O) groups and not morethan one C(═NR₂₅) group, and each ring system may itself be mono- orpoly-substituted by C₁-C₆alkyl, C₁-C₆haloalkyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl, C₂-C₆alkynyl, C₂-C₆haloalkynyl, C₁-C₆alkoxy,C₁-C₆haloalkoxy, C₃-C₆alkenyloxy, C₃-C₆alkynyloxy, mercapto, amino,hydroxy, C₁-C₆alkylthio, C₁-C₆haloalkylthio, C₃-C₆alkenylthio,C₃-C₆haloalkenylthio, C₃-C₆alkynylthio, C₁-C₃alkoxy-C₁-C₃alkylthio,C₁-C₄alkylcarbonyl-C₁-C₃alkylthio, C₁-C₄alkoxycarbonyl-C₁-C₃alkylthio,cyano-C₁-C₃alkylthio, C₁-C₆alkylsulfinyl, C₁-C₆haloalkysulfinyl,C₁-C₆alkylsulfonyl, C₁-C₆haloalkylsulfonyl, aminosulfonyl,C₁-C₂alkylaminosulfonyl, N,N-di(C₁-C₂alkyl)aminosulfonyl,di(C₁-C₄alkyl)amino, halogen, cyano, nitro or phenyl, it being possiblefor the phenyl group in turn to be substituted by hydroxy,C₁-C₆alkylthio, C₁-C₆haloalkylthio, C₃-C₆alkenylthio,C₃-C₆haloalkenylthio, C₃-C₆alkynylthio, C₁-C₃alkoxy-C₁-C₃alkylthio,C₁-C₄alkoxycarbonyl-C₁-C₃alkylthio, C₁-C₄alkoxycarbonyl-C₁-C₃alkylthio,cyano-C₁-C₃alkylthio, C₁-C₆alkylsulfinyl, C₁-C₆haloalkysulfinyl,C₁-C₆alkylsulfonyl, C₁-C₆haloalkylsulfonyl, aminosulfonyl,C₁-C₂alkylaminosulfonyl, N,N-di(C₁-C₂alkyl)aminosulfonyl,di(C₁-C₄alkyl)amino, halogen, cyano or nitro, and the substituents atthe nitrogen atom in the heterocyclic ring being other than halogen, andtwo oxygen atoms not being located next to one another; R₂₅ is hydrogen,hydroxy, C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxy, C₁-C₆alkylcarbonyl,C₁-C₆alkoxycarbonyl or C₁-C₆alkylsulfonyl; and n₁ is 0, 1 or 2; and n₆is 0, 1 or 2; or an agronomically acceptable salt, enantiomer, ortautomer of such a compound.
 2. A herbicidal and plant-growth-inhibitingcomposition, comprising a herbicidally effective amount of a compound offormula I according to claim 1 on an inert carrier.
 3. A method ofcontrolling undesired plant growth, which method comprises applying acompound of formula I according to claim 2, or a composition comprisingsuch a compound, in a herbicidally effective amount to a plant or to thelocus thereof.
 4. A method of inhibiting plant growth, which methodcomprises applying a compound of formula I according to claim 2, or acomposition comprising such a compound, in a herbicidally effectiveamount to a plant or to the locus thereof.